Process and hydrocarbon soluble saline hydride catalyst for hydrogen mediated saline hydride initiated anionic chain transfer polymerization and polymer distribution compositions produced therefrom

ABSTRACT

This invention relates to processes for forming hydrogen mediated saline hydride initiated anionic polymer distributions via novel polymerization conditions in which molecular hydrogen is a chain transfer agent and a Lithium Aminoalkoxide Complexed Saline Hydride (LOXSH) forms an anionic polymer chain initiating species by addition of saline hydride to an anionically polymerizable hydrocarbon monomer. This invention further relates to polystyrene compositions having greatly improved microstructures free of co-product polymer chain distributions. This invention also relates to novel hydrocarbon soluble saline hydride catalyst and reagent compositions useful in conducting the hydrogen mediated saline hydride initiated polymerizations of this invention. This invention further relates to hydrocarbon soluble lithium hydride catalysts and reagent compositions formed from dimethylaminoethanol, an alkyllithium reagent and molecular hydrogen. It also relates to the catalyst forming processes, the use of the catalyst in hydrogen mediated anionic polymerization of styrene (HMAPS) and the resulting low molecular weight polystyrene distributions of low asymmetry and high “head to tail” microstructure.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application, filed Feb. 25, 2021, is a Divisional applicationclaiming the benefit of U.S. patent application Ser. No. 16/091,795filed Oct. 5, 2018, which is a national entry under 35 U.S.C. § 371 ofand claims the benefit of Patent Cooperation Treaty Application No.PCT/US2017/025926, which claims priority to and the benefit of U.S.Provisional Application 62/318,258, filed Apr. 5, 2016, and U.S.Provisional Application 62/320,003, filed Apr. 8, 2016, the entirecontents and substance of all of which are hereby incorporated byreference as if fully set forth below.

TECHNICAL FIELD

This invention relates processes for forming hydrogen mediated salinehydride initiated anionic polymer distributions via novel polymerizationconditions in which molecular hydrogen is a chain transfer agent and aLithium Aminoalkoxide Complexed Saline Hydride (LOXSH) forms an anionicpolymer chain initiating species by addition of saline hydride to ananionically polymerizable hydrocarbon monomer; all of which takes placein a very efficient to highly efficient catalytic cycle where thekinetic chain length distribution is mediated by hydrogen or otherwiseset by the relative feed rate of hydrogen to monomer. This inventionfurther relates polystyrene compositions having greatly improvedmicrostructures free of co-product polymer chain distributions. Thisinvention also relates novel hydrocarbon soluble saline hydride catalystand reagent compositions useful in conducting the hydrogen mediatedsaline hydride initiated polymerizations of this invention. Thisinvention further relates to hydrocarbon soluble lithium hydridecatalysts and reagent compositions formed from dimethylaminoethanol(a.k.a. dimethylethanolamine), an alkyllithium reagent and molecularhydrogen, it also relates the catalyst forming processes, the use of thecatalyst in hydrogen mediated anionic polymerization of styrene (HMAPS)and the resulting low molecular weight polystyrene distributions of lowasymmetry and high “head to tail” microstructure.

BACKGROUND OF THE INVENTION

Low molecular weight—M_(w)<<4000 Daltons—polystyrene compositions areuseful in a variety of applications both in their end use such aspolymer slip reagents (see EPO 741147) or as substrate precursor's forfurther synthetic derivatization. Such synthetic derivatizations

entail aromatic electrophilic substitution reactions (see: U.S. Pat. No.8,217,120B2 “Functionalized styrene oligomers and polymers”). Anionicchain transfer polymerization of polystyrene provides an economicbenefit due to the cost-effective efficient use of the anionic chaintransfer catalyst when forming low molecular weight polystyrenecompositions due to substantial reduction in the amounts oforganolithium reagents and other alkali earth metal regents used informing the chain transfer initiators and catalysts. Accordingly, methylbenzene compounds (toluene). polymethylbenzene compounds (xylenes,mesitylene, durene, etc.) are excellent chain transfer agents forforming low molecular weight polystyrene compositions suitable forfurther synthetic elaboration. Such methyl benzene chain transfer agentsowe in part their effectiveness to the chemical fact that the pK_(a) oftheir most acidic carbon hydrogen bond is at least one order ofmagnitude lower (i.e. they are more acidic) than that of the conjugateacid of a poly(styryl) anion. More complex alkyl substituted benzeneorganic chain transfer agents, in particular ethylbenzene (EB) which isthe simplest, have been reported (EPO 741147) or at least suggested tobe suitable organic chain transfer agents for forming anionic chaintransfer styrene distributions when using a catalyst formed frompotassium t-butoxide, sec-butyllithium andN,N,N′,N′-tetramethylethylenediamine (TMEDA).

Alkyl substituted aromatic hydrocarbon chain transfer reagents ingeneral make up a relatively large percentage of the molecular weight ofsaid anionic chain transfer compositions for low molecular weightcompositions. For example an anionic chain transfer composition havingM_(w)=716 formed from toluene and styrene, on a weight average basissaid composition is comprised of 12.8% toluene. Similarly for an anionicchain transfer composition having M_(w)=730 formed from ethylbenzene andstyrene, on a weight average basis said composition is comprised of14.5% ethylbenzene. It can be desirable to form low molecular weightpolystyrene compositions that are essentially free (comprising less than2 wt % of the composition) of such organic chain transfer agents.Furthermore it can be desirable that the amount of an anionic chaintransfer agent—whether organic or inorganic—also comprise less than 2 wt% of the resulting polystyrene composition. For an anionic chaintransfer process each and every chain incorporates exactly one organicchain transfer initiator monomer added to the monomer(s) to bepolymerized. Alkyl substituted aromatic hydrocarbons have molecularweights that are ≥92.14 Daltons—the formula weight of toluene. Thus itis a simple mathematical fact that the lowest M_(w) of an anionic chaintransfer distribution comprised of ≥2 wt % of toluene is given byM_(w)≥92.14±0.02=4607 Daltons. All anionic chain transfer compositionsformed from alkyl substituted aromatic chain transfer agents (e.g.ethylbenzene or xylenes) of higher molecular weights would have to havea minimum M_(w) that is greater than 4607 Daltons.

In theory an anionic chain transfer compositions formed from ethylbenzene and styrene would have a structure identical to anionicallypolymerized styrene compositions formed exclusively from styrenemonomer. However quite to the contrary, it has been discovered thatethylbenzene when used as a chain transfer agent under prior artconditions such as in EP O 741 147, such process conditions providepolystyrene compositions of non-uniform microstructure with addedimpurities and impurity distributions (see FIG. 12). Such undesiredimpurities and impurity distributions arise from chain isomerization andfragmentation processes (see FIGS. 1 and 2). Consequently the chainlength distribution of compositions such as the Examples of EP O741 147are in toto distributions that includes undesired ensembles of isomericpolymer microstructures—microstructures less desired for aromaticelectrophilic substitution reactions. Such impurities and impuritydistributions can be problematic in further derivatization of suchanionic chain transfer compositions. A high level of any discreteimpurity—an amount of 1000 ppm or greater—is undesirable in terms ofproducing a product for market. Thus it is desired to polymerize styreneto form low molecular weight polystyrene compositions having greatlyreduced or essentially no undesired polymer microstructure features orimpurity fragments and said compositions are desired to be comprisedsolely (/98 wt %) of polymerized styrene monomer.

The wt % ethylbenzene of the anionic chain transfer styrenic reactiondistributions of EP O 741 147 have been calculated (wt %EB=106/M_(w)*100%) and presented in Table I below. From the experimentaldetails as presented in Table I, it can be seen by comparison of EP 0741 147 Examples 2-7 that only Example 4 produced a polymeric anionicchain transfer styrenic reaction distribution (ACTSR distribution)having limited breadth (standard deviation) and small polydispersity.Minor changes in the relative feed rates or charges or bothsimultaneously as reported, resulted in ACTSR distributions having verylarge standard deviations and having polydispersity that increasesignificantly, and in some cases astronomically (e.g. EP O 741 147Examples 2, 3 and 7). Thus, it can be seen that from such experimentaldetails, a very narrow and limited process window for producingdistributions with narrow breath, i.e., small standard deviation (σ_(n))is provided.

From the experimental details of EP 0 741 147 A1, as presented in TableI below, it can be seen by comparison of EP 0 741 147 Examples 2-7 andD, that only Example 4 produced an anionic chain transfer styrenicreaction distribution (ACTSR distribution) having limited breadth(standard deviation) and small polydispersity. Minor changes in therelative feed rates or reagent charges as reported, or bothsimultaneously, resulted in ACTSR distributions having very largestandard deviations and having polydispersity that increasesignificantly, and in some Examples, astronomically. Thus, it can beseen that from such experimental details, a very narrow and limitedprocess window for producing distributions with narrow breath, i.e.,small standard deviation σ_(n) is provided. Investigations of this priorart technology reveals that the process technology suffers from theundesirable formation of a catalyst composition of low or limitedsolubility in the hydrocarbon reaction medium. It is desirable to have acatalyst system that has greatly improved hydrocarbon solubility withimproved utilization or efficiency producing lower molecular weightstyrenic distributions of more uniform, if not completely uniform,polymer chain length distribution microstructure.

TABLE I Prior Art EPO 741147 Anionic Chain Transfer StyrenePolymerization w/Ethylbenzene as the Chain Transfer Agent EPO 741147Example # 1 2 3 4 5 6 7 D Cyclohexane Diluent (ml) 0 1558 1558 1558 15581558 1558 0 g Cyclohexane/g Styrene 0 0.36 0.36 0.96 0.96 0.96 0.36 0Mole K:Mole Li 1:1 1:1 1:1 1:1 1:1 1;1 1;1 0:1 Mole Styrene/mole 0.447.03 7.03 7.09 14.18 14.18 18.86 0.44 Ethylbenzene Mole Styrene/hr/mole0.02 0.39 1.17 1.18 2.36 2.36 1.05 0.024 Ethylbenzene MoleStyrene/hr/mole 10.67 10.66 31.98 32.06 64.12 32.06 21.30 10.67 LithiumWt % Ethylbenzene 40.5% 0.5% 0.3% 7.1% 2.2% 2.8% 0.3% 2.2% M_(n) 164 8761212 932 2137 1736 596 2700 M_(w) 262 19700 41800 1500 4830 3750 333004900 M_(z) NR NR NR NR NR NR NR NR PD 1.60 22.50 34.50 1.61 2.26 2.1655.90 1.81 Standard Deviation 127 4060 7013 728 2399 1870 4414 2437σ_(n) = (M_(w)M_(n) − M_(n) ²)^(1/2)

As noted above in Table I EP 0 741 147 Example D a monometallic lithiumbased catalyst system is ineffective, or at best very inefficient, atcatalyzing anionic chain transfer polymerization of styrene withethylbenzene. What is more is that it is well documented thatmonometallic TMEDA butyllithium catalyst forming reagents exhibit poorregioselectivity with regard to the metalation of ethylbenzene. In apaper authored by Broaddus (Broaddus, C. D., J. Org. Chem. 1970, 35,10.) it is reported that the a position hydrogen of ethylbenzene formsthe benzylic lithium in only 38%, with the ortho-lithiation occurring tothe extent of 9%, the meta-lithiation occurring to the extent of 36% andthe para-lithiation occurring to the extent of 17%. Thus the prior artteaches that monometallic lithium catalyst forming reagents thatlithiate ethylbenzene would produce many different polymermicrostructures that are regioisomeric chain length distributions withregard to the initiating ethylbenzene moiety. Thus it is desirable tohave a highly efficient chain transfer polymerization process of styrenewhere the pathway that entails an anionic chain transfer step involvingmetalation of ethylbenzene (whether ethylbenzene is added or formed insitu) is reduced if not eliminated and yet still forms the desiredanionic chain transfer distribution chain length microstructure. Such aprocess once realized would entail direct one step hydride addition(e.g. a one-step hydrolithiation reaction) to a styrene or otherstyrenic or other vinyl aromatic monomer. Such a hydrolithiated monomershould be capable of efficiently initiating polymerization of moremonomer with subseqent chain transfer from molecular hydrogen. Such aprocess requires consistently and repeatedly reforming the hydridecatalyst in an active form. Thus such a hydrogen mediated saline hydrideinitiated polymerization process should be high yielding of dimer andabove and feature catalyst efficiencies where the amount of catalyst isreduced from 200% to 10,000%.

Investigations of this prior art technology (in connection with theComparative Examples 46-48 of WO2010065468A1) have revealed that theprocess technology suffers from undesirable formation of a catalystcompositions of low or limited solubility in the hydrocarbon reactionmedium. Thus minor changes in reaction charges can result in drasticchanges in product distributions which arise from decreased catalystavailability. The processes of EP O 741 147 rely on very slow relativefeed rates conducted over long feed times (6 to 18 hours) in order toattempt to equilibrate living and dead polymer chains. A primary problemwith ethylbenzene as a chain transfer agent is that the pK_(a) ofethylbenzene is of the same order of magnitude if not equal to theapproximate value of that of the conjugate acid of a poly(styryl) anion.It is desirable to have a new catalyst and anionic chain transferpolymerization conditions that can provide soluble catalyst compositionssuch that in turn provide the advantages of: 1) lower molecular weightpolystyrene distributions with M_(n)<930 even<700 Daltons; 2) moreeconomical use of reagents; and 3) shorter time periods with moreefficient use and productivity of the polymerization reactor. Thehydrogen mediated saline hydride initiated process technology of thisinvention in fact provides such advantages.

Polymerization of styrene under a hydrogen atmosphere is known forZeigler Natta polymerization of styrene (Murahashi, S.; Nozakura, S.;and Utsuhara Y. “Polymerization of Styrene with the Ziegler-NattaCatalysts in the Presence of Molecular Hydrogen.” Bulletin of theChemical Society of Japan 196033431). Additionally there is at least onereport of for metallocene polymerization of styrene under a hydrogenatmosphere (Ref. 14: Tomotsu, N., Kuramoto, M., Takeuchi, M., & Maezawa,H. (1996). Metallocenes 1996, 96, 211.(i) Chien, J C W.; in Tomotsu, N.,et al. “Syndiospecific Polymerization of Styrene.” Journal of MolecularCatalysis A: Chemical 1998128.1167). In both polymerization chemistriesformation of ethylbenzene, the hydrogenation product of styrene ismentioned. Thus Utsuhara and coworkers reported that isotacticpolystyrenes of the low molecular weight could be obtained in thepresence of hydrogen, although in addition to this there was foundanother reaction which is competitive to the polymerization reaction, i.e. hydrogenation of styrene to ethylbenzene. In both approaches tohydrogen mediation of styrene polymerization—Ziegler Natta andmetallocenes catalysis—ethylbenzene is kinetically inert and representsan unrecoverable yield loss.

Deffieux and coworkers report the hydrogenolysis of poly(styryl)lithiumdistributions (50° C. H₂ 1 atm) leading to the in situ formation oflithium hydride capable of a largely inefficient reinitiation of styreneanionic polymerization at 100° C. (Ménoret, S., Deffieux, A., & Desbois,P. “Initiation of retarded styrene anionic polymerization usingcomplexes of lithium hydride with organometallic compounds.”Macromolecules, (2003) 36, 5988). Deffieux further reports that:“However, the slow addition of LiH to styrene with respect topropagation yields incomplete initiation.” Deffieux reports that withaddition of an added organometallic Lewis acid reagent (n,sec-Bu₂Mg, orBuMgOBT or i-Bu₃Al) the solubility and reinitiation efficiency of theLiH is improved but the catalyst efficiency is only between 50 and 150%.Furthermore the bimetallic complex formed decreases the rate oftermination and the half-life of the active or livingpoly(styryl)lithium species is greatly increased from 40 min foruncomplexed poly(styryl)lithium to 34 hours for the bimetallic complexedpoly(styryl)lithium at 50° C. in cyclohexane and 1.1 atm H₂. In factthey report that it requires 50 atmospheres (ca. 50 bar) H₂ to restorethe half-life of the living poly(styryl)lithium species to 50 minutes.Deffieux and co-workers teach that soluble lithium hydride is apotential initiator of styrene polymerization:

-   -   “Lithium hydride, as long as it remains soluble, is a potential        initiator of styrene anionic polymerization, at least at 100°        C., even in nonpolar solvent. The efficiency of this initiator        is improved by complexation with organometallic derivatives        which first ensure its solubility and then reduce the styrene        propagation rate. When n,sec-Bu₂Mg is used as additive, Li—H        bonds are not the real initiating sites, the polymerization        proceeding after a ligand exchange between the two metal atoms.”    -   “At high temperature, H₂ acts as a chain transfer agent in        styrene anionic polymerization. However, to be efficient, its        concentration in the medium should be high in order to shift the        equilibrium toward the formation of metal hydride. This requires        high hydrogen working pressures.”        However Deffieux and coworkers require complexation of LiH with        Lewis acids such as dialkylmagnesium reagents, aluminum akyls        and/or alkylaluminum hydrides to solubilize the LiH. Such Lewis        acid complexed LiH reagents so formed are not efficiently        reduced once used to initiate styrene polymerization.        Consequently such Lewis acid complexed poly(styryl)lithium        chains are not efficiently reduced nor does their reduction        effectively regenerate a highly active or super active form of        LiH initiator.

It is documented in the literature that only two highly soluble Group 1metal hydrides free of Lewis acid complexing agents are known (see:Stasch, A. and Fohlmeister, L. Aust. J. Chem. 2015, 68, 1190-1201; andLiptrot, D. J., Springer Thesis: Group 2 Mediated Dehydrocoupling,Chapter 2. Group 1-Group 2 Bimetallic Alkyls and Hydrides, SpringerInternational Publishing, 2016, pp. 41-61). These are: (1) the “superaggregate” [(t-BuOLi)₁₆(LiH)₁₇] generated photolytic decomposition of amixture of butyllithium lithium t-butoxide (Thomas, D. et. al., J. Am.Chem Soc. 1997, 119, 11998; and Thomas, D. et. al., Angew. Chem. Int.Ed. 1998, 37, 1537); and (2) Stash's hydrocarbon soluble LiH complex,[(DipNPPh₂)₄Li₈H₄] (Dip, 2,6-iPr₂C₆H₃), prepared by the application ofphenylsilane to a reactive metal precursor (Stasch, A. Angew. Chem. Int.Ed. 2012, 51, 1930.) However this hydrocarbon soluble LiH reagent is notreactive or available enough to hydrolithiate the very active speciesdiphenylacetylene or 1,1-diphenylethylene. Thus one of ordinary skill inthe art would understand that [(DipNPPh₂)₄Li₈H₄] would not likelyhydrolithiate an even less active styrenic or other less active vinylaromatic monomer and consequently would not initiate polymerization ofsuch monomers. Stash also reports the formation of “initially clearsolutions” of LiH/Li(pz) (pz=3,5-di-tert-butyl-1H-pyrazole) which turnmilky likely due to formation of colloidal LiH. Such “initially clearsolutions” are prepared by treating 3,5-di-tert-butyl-1H-pyrazole (pzH)with more than one equivalent of n-butyllithium in aromatic or aliphaticsolvents, followed by addition of phenyl- or diphenylsilane to convertthe excess alkyllithium groups to hydrides. Stash has prepared the firstsoluble NaH complex [(pz)₆Na₇H] by the same synthetic strategy as theLiH/Li(pz) methodology again using the sterically demanding pyrazolateligand (pz) by the reaction of [Na(pz)], [Na(nBu)] and diphenylsilane inaromatic solvents. The application of the same synthetic strategy usedto produce [(pz)₆Na₇H] to form a KH hydride analogue resulted only inthe formation and separation of crystalline polymeric [K(pz)]. Thus astable aliphatic and/or cycloaliphatic and/or aromatic hydrocarbonsoluble monometallic, bimetallic or polymetallic alkali (Group 1) metalhydride formed directly from molecular hydrogen, H₂, is heretoforeunknown.

In their publication (Stasch, A. and Fohlmeister, L. Aust. J. Chem.2015, 68, 1190-1201) teach the following:

-   -   “Well-defined hydride complexes purely of Group 1 metals are        very rare and are in fact only known for lithium and sodium so        far . . . . Most isolated compounds involving alkali metals and        hydridic hydrogen centres are mixed-element systems and are best        described as ‘ate’-type complexes in which the strongest        interaction of the hydride ligand is with the non-alkali metal        centre or metalloid . . . . This makes the majority of these        ‘ate’ complexes covalent hydride complexes. The most prominent        examples in this compound class are perhaps LiAlH₄, NaBH₄, and        other related commercial derivatives such as L-selectride®,        N-selectride®, and K-selectride® (lithium, sodium, potassium        tri-sec-butyl(hydrido)borate), or derivatives with sterically        demanding ligands.” emphasis added.

Thus it should be clear that the prior art Lewis acid complexed lithiumhydride, sodium hydride and potassium hydride initiators (such as thoseutilized by Deffieux and co-workers in their retarded styrene anionicpolymerizations) are covalent hydrides and not among the saline hydridecatalyst of this invention.

In contrast to covalent hydrides, saline hydrides (meaning ionichydrides) are defined by the presence of hydrogen as a negativelycharged ion, H⁻, in combination with an alkali metal or alkaline earthmetal. With regard to the addition to styrene with concomitantpolymerization of saline hydrides free of complexing Lewis acids,Deffieux and coworkers provide the following background (ibid):

-   -   “To the best of our knowledge, very few papers deal with anionic        polymerization of vinylic monomers initiated by metal hydrides.        Williams briefly mentioned one styrene polymerization experiment        initiated by NaH in hexane at 25° C. However, the initiation        efficiency was very low and the conversion reached only 90%        after 3 days.”

Liao and coworkers reported a form of highly active alkali metalhydrides having nanometric (≈20 nm) particle size distributions (Liao,S.; et. al. Journal of Molecular Catalysis, 1993, 84, 211.) In thispaper Liao reports formation of highly active saline hydrides (HASH)from the corresponding alkali metal and hydrogen (1 atm) in THF (40° C.)catalyzed by TiCl₄ and naphthalene. Complete conversion to the salinehydride required 2 hours for LiH*, 4 hours NaH* and 28 hours for KH*(the * denoting highly active or super active hydride). These nanometricsaline hydrides were found to have some utility in the dechlorinationand debromination of certain arylhalides. They were also reported to beactive as co-catalyst for the hydrogenation of olefins such as 1-hexenewhen used in certain transition metal complexes. Turnover frequencies inthe range of 0.003 to 45.3 s⁻¹ were reported. Thus highly active alkalimetal hydrides (50-300 mol) when used in conjunction with a transitionmetal catalyst (1 mol) only reduces olefins, no disclosure ofpolymerization or even dimerization of the olefin is made.

Other applications of nanometric size alkali metal hydrides were laterreported by Liao and coworkers (Liao, S.; et. al. Synth. Comm. 1997,273977.) Such applications include the reduction of carbonyl carbon toaldehydes and/or alcohols of benzaldehyde, methyl benzoate, acrolein andthe methyl and n-butyl ester of acrylic acid. The reactions wereconducted in refluxing THF using a stoichiometric excess of highlyactive saline hydride—either as NaH* or as KaH*—and reactions times of0.25 to 15 hours. Of particular interest are the reduction of acrolein(0.3 hour) and methyl acrylate (0.25 hour) with NaH* to yield allylalcohol in 97% and 96% yield respectively. In another publication Liaoand co-workers report that heat treated nanometric LiH, NaH and KHcomplexed with Cp₂TiCl₂, CP₂TiCl₂-MH (M=Li, Na or K), can be used as acatalyst to hydrogenate either styrene (M=Li or Na) or Octene (M=K).Nanometric KH with Cp₂TiCl₂ under one atmosphere H₂ did not hydrogenatestyrene instead initiated polymerization to form very high molecularweight (MW) polystyrene (M_(w)=200,000) with a wide range of meltingpoints T=160-180° C. It was further found that nanometric KH alonepolymerized styrene, one of ordinary skill in the art would understandthat such high MW anionic polystyrene (APS) compositions are the resultof inefficient initiation and consequently resulting in formation ofonly very few living polymer chains which rapidly incorporate thestyrene monomer at the expense of the remaining insoluble nanometric KH.

Zhang and co-workers report highly active catalysts for thehydrogenation of styrene (2 ml) in toluene (9 ml) under hydrogenatmosphere at −17° C. to 42° C. (Zhang, M.; et. al. Catal Lett 2008,124, 146). The highly active catalysts were formed from nanometric sizedsodium hydride (20 mg, 8.7×10⁻⁴) and 12 different Lewis base freetitanocene complexes (0.5 mL of 4×10⁻⁴ mol/L i.e. 2×10⁻⁷mol)—NaH*/Ti=4350). Uptake of hydrogen was not observed in two otherexamples where the titanocene complex contained a coordinating oxygen(ether) or nitrogen (tertiary amine) species. Despite the large excessof NaH* to the titanocene catalyst, no report or even mention is made ofthe polymerization of styrene much less any form of chain transferchemistry.

The preparation of super active—extremely finely divided—forms oflithium, sodium and potassium hydrides were reported by Schleyer andco-workers (Schleyer, P. v. R.; et. al. J. Org. Chem. 1987. 52, 4299;and Schleyer, P. v. R.; et. al. Angew Chem Int. Ed. Engl. 198625465.)The preparation of these super active saline hydrides (SASH) as a finesuspension entailed the hydrogenation of the corresponding alkali metalalkyls in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA)in hexanes. Formation of super active LiH* was conducted between 30° and35° C., super active NaH* was prepared under cryogenic conditions (−10°C. to −15° C.), and super active KH* was reported to be formed at −20°to −25° C. The application of the hydrides to organic synthesis wasexplored by Schleyer and reported in the above cited open literaturepapers. Most of the synthetic reactions (metalations, additions andreductions) were conducted under cryogenic conditions with temperaturesas low as −90° C. with a few reactions conducted between roomtemperature and 50° C. There were also no disclosures in Schleyer to usethe hydrides for polymerization of styrenic or vinyl, much less hydrogenmediation of such polymerization processes.

Harder and coworkers have reported that styrene can be catalyticallyhydrogenated (20° C., 20 atmospheres H₂, 15 hours in benzene) with 2.5mole % of the organocalcium catalyst [DIPPnacnacCaH.THF]₂ initiallyformed from phenylsilane (see. Harder, S., Speilman, J., Buch, F. Angew.Chem. 2008, 120, 9576 also published as Angew. Chem. Int. Ed. 2008, 47,9434). The hydrogenation produced ethylbenzene in 85% yield along with a15% yield of oligomers comprised mostly of styrene dimer with traces ofstyrene trimers and tetramers. Harder further reports 1,1-diphenyletheneis reduced at a low conversion to yield 14% Ph₂CHCH₃ and 7% dimer in acatalyst formed from 5 mole % butyllithium/TMEDA complex at 20° C., 20atmospheres H₂, 15 hours in benzene. With regard to this reaction theauthors make the following statement:

-   -   “The reaction catalyzed by commercially available nBuLi/TMEDA        proceeded only to low conversion . . . suggesting that, at lower        H₂ pressures, the heavier alkaline-earth metal complexes are the        more efficient catalysts.”

Tetrahydrofuran soluble forms of magnesium hydride were produced byAshby and coworkers from ortho-substituted (2,6-dimethyl- and2,6-di-isopropylphenoxides) aryloxymagnesium reagents and an active formof solid magnesium hydride. Tetrahydrofuran insoluble forms of magnesiumhydride resulted from alkoxymagnesium reagents and the solid magnesiumhydride reagent (see Ashbey, E. C., Goel, A. B., Lin, J. J. TetrahedronLetters, 1977, 3133.) Ashby also reported the formation oftetrahydrofuran soluble dialkylaminomagnesium hydrides from a series ofbulky dialkyl and bulky alkylsubstituted cycloalkyl secondary amines byreaction with an active form of solid magnesium hydride. Said activeform of magnesium hydride was prepared by the reduction ofdimethylmagnesium with LiAlH₄ in diethyl ether. Thus the bulky dialkyland bulky alkylsubstituted cycloalkyl secondary amines are reacted withdimethylmagnesium to form the bis(dialkylmagnesium)magnesium compoundswhich were in turn reacted in THF with the active form of magnesiumhydride (see Ashbey, E. C., Goel, A. B., Lin, J. J. J. Or. Chem., 1978,43, 1564. Such aminomagnesium hydrides if they can initiatepolymerization would likely initiate polymerization to some extent viaaddition of amide to the monomer and result in an incorporation of anundesired amine functionality in the resulting polymer distribution.

Michalczyk report the formation in ethereal or hydrocarbon solvents inthe presence of “appropriate ligands” the formation of a precipitatedform of magnesium hydride MgH₂L_(x). Such appropriate ligands includedtetrahydrofuran, ethylene glycol dimethyl ether, and TMEDA. The reducingagent employed was phenylsilane (see Michalczyk, M. J. Organometallics,1992, 11, 2307). In a recent review entitled “Molecular Early Main GroupMetal Hydrides: Synthetic Challenge, Structures and Applications” Harderreviews the state of the art of the controlled synthesis of well-definedGroup 1 and Group 2 metal hydrides. In general such hydrides have beenprepared by the methods outlined above which include: photo-degradation;reactions of active hydrides to form “ate-complexes” such as thearyloxymagnesium hydride as well as the dialkylaminomagnesium hydridesreported by Ashby; Harder's [DIPPnacnacCaH.THF]₂ initially formed fromphenylsilane; and Stasch's soluble lithium hydride complex formed fromphenylsilane. Additionally Harder reviews a host of hydrides formed fromthe thermal decomposition of magnesite complexes [(iPr₂N)₃Mg⁻]M⁺(M⁺=Na⁺, K⁺). A common feature of all approaches to forming solublesaline hydride compositions is the use of bulky (usually isopropylatedligands) to achieve solubility. In all cases except for the poorlycatalytic species formed during the hydrogenation of styrene toethylbenzene (85% yield) such as the example using [DIPPnacnacCaH.THF]₂(which again was initially formed from phenylsilane), the saline hydridecomplexes were formed from some other reagent other than molecularhydrogen. Only Scheyer's insoluble forms of super active saline hydrides(SASH) are formed directly from molecular hydrogen as the initialreducing reagent.

Accordingly, the prior art does not disclose the use of a lithiumaminoalkoxide complexed saline hydride (LOXSH) species for anionic-chaintransfer polymerization of vinyl aromatic monomers such as a styrenicmonomers. In fact the prior art does not even anticipate the formationof the LOXSH catalysts, especially as hydrocarbon soluble species andparticularly when formed from simple non bulky ligands much lessdirectly from H₂. The inventor has discovered these hydrides as well asthe surprising fact that the use of these novel hydrides can catalyzehydrogen mediated saline hydride initiated polymerization process.Accordingly, this invention provides a process for the efficient anionicchain transfer polymerization of vinyl aromatic monomers under mildtemperatures (e.g., about 20° C. to less than 100° C.) where hydrogen isthe principal or sole chain transfer agent. Said process can beconducted at relatively low to very low hydrogen partial pressures.Furthermore the inventor has discovered that the novel polymerizationcatalysts of this invention provide low molecular weight anionicallypolymerized styrene distributions comprised solely of styrene (/98 wt %styrene) with unique, uniform and beneficial “Head to Tail”microstructure essentially if not completely free of quaternary carbonsin the polymer microstructure. Thus such polystyrene distributions haveless than 3.0 wt %, preferably less than 2.0 wt %, and more preferablyless than 1.0 wt % of the polystyrene polymer chains with a quaternarycarbon in the polymer chain backbone. Thus such compositions in totohave less than 1000 ppm even less than 200 ppm and even less than 20 ppmquaternary carbons present. Likewise the polystyrene compositions ofthis invention have less than 1.0%, preferably less 0.5% and mostpreferably less than 0.1% of polymer chain distributions or impuritiesresulting from fragmentation of the desired anionic chain transferpolystyrene distribution.

DEFINITION OF CHEMICAL ACRONYMS AND NUMERICAL TERMS

PTA is an acronym for a general class of polytertiaryamines used aspromotors, the usage of “.XPTA” where X is a positive number andindicates the number, whole or fractional, of moles of PTA complexed toa catalyst composition.

TMEDA is an acronym for N,N,N′,N′-tetramethylethylenediamine a PTA, theusage of “.XTMEDA” where X is a positive number and indicates thenumber, whole or fractional, of moles of TMEDA used and/or complexed toa catalyst composition.

PCAH is an acronym for a the general class of polarizing complexingagents used in forming the catalyst of this invention denoting thepolarizing complexing agent as the neutral alcohol, the usage of [PCA⁻]denotes the polarizing complexing agent as the alkoxide having given upone proton to a more basic chemical species. The use of [PCA⁻]hereinafter is thus for convenience in showing that an alkoxide has beenformed from PCAH. The use of in a formula such as [PCA⁻]_(x)M_(y)H_(z)is to be interpreted as a neutral catalyst complex or aggregate wherethe charge of the y-metal atoms is balanced by the charge of x [PCA⁻]anions in combination with z hydride ions. It is to be understood thatthe use of [PCA⁻]_(x)M_(y)H_(z) is for the entire catalyst formulae andin would include any potential “ate’ complex such as:

[[PCA⁻]_(x)M_(y)H_(z−n)]^(n+)[[PCA⁻]_(x)M_(y)H_(z+n)]^(n−).

DMEAH is an acronym for N,N-dimethylethanolamine (Synonym:N,N-Dimethyl-2-hydroxyethylamine, N,N-Dimethylethanolamine) as theneutral aminoalcohol, the usage of [DMEA⁻] representsN,N-dimethylethanolamine as an alkoxide having given up one proton to amore basic species.

DMAEOEH is an acronym for 2-N,N-dimethylaminoethoxyethanol(N(CH₃)₂CH₂CH₂O—CH₂CH₂OH) as the neutral amino ether-alcohol, the usageof [DMAEOE⁻] represents N,N-dimethylaminoethoxyethanol as an alkoxidehaving given up one proton to a more basic species.

MEOEH is an acronym for 2-methoxyethanol as the neutral ether-alcohol,the usage of [MEOE⁻] represents 2-methoxyethanol as an alkoxide havinggiven up one proton to a more basic species.

The efficiency (Eff_(CT)) of an anionic chain transfer process is givenby the expression:

Eff_(CT).=M_(n Th)/M_(n exp);

where M_(n Th) is the theoretical number average molecular weight, andthe term M_(n exp) is the number average molecular weight obtained inthe actual run or process. The percent efficiency is obtained bymultiplication of the efficiency by 100%.

A brief resume of parameters used to describe molecular weightdistributions and the equations that define them are presented in TableII below. (A. Rudin, The Elements of Polymer Science and Engineering,Academic Press, Orlando, 1982, pp. 54-58). The number average DP(DP_(n)) is calculated using M_(n as) 100% polystyrene compositions.

TABLE II Parameter Equation DP_(n), Number average degree of DP_(n) =(M_(n) − 2)/104 (for a polystyrene polymerization distribution) M_(n),Number average molecular weight M_(n) = (Σ M_(i)n_(i)) M_(w), Weightaverage molecular weight M_(w) = [(Σ M_(i) ²n_(i))/M_(n)] M_(z),z-Average molecular weight M_(z) = (Σ M_(i) ³n_(i))/Σ M_(i) ²n_(i) PD,Polydispersity Index (also PDI) PD = (Σ M_(i)n_(i))/[(Σ M_(i)²n_(i))/M_(n)] Variance V = (M_(w)M_(n) − M_(n) ²) Standard Deviation,σ_(n) σ_(n) = √(M_(w)M_(n) − M_(n) ²) Skewness, _(n)U₃ _(n)U₃ =M_(z)M_(w)M_(n) − 3M_(n) ²M_(w) + 2M_(n) ³ Asymmetry, _(n)α₃ _(n)α₃ =(M_(z)M_(w)M_(n) − 3M_(n) ²M_(w) + 2M_(n) ³)/σ_(n) ³

SUMMARY OF THIS INVENTION

The hydrogen mediated saline hydride initiated polymerization (HMSHIP)processes of this invention features: a) the novel ability of solublesaline hydride species to rapidly add to a vinyl aromatic monomer toform an initiating species; b) the novel high efficiency in which theaddition of the saline hydride species to monomer takes place and thusallows competition between the reinitiation step to compete with thepropagation reaction step to grow the active transient livingpoly(styryl)anion chains thus maintaining a constant or near constantnumber of active growing chains; and c) the capacity of chain transferfrom hydrogen under the mild and novel process conditions to terminatesuch living poly(styryl)anionic species and regenerate the salinehydride in a form capable of effectively and efficiently reinitiatingthe polymerization process. Thus this invention relates to a process ofconducting hydrogen mediated saline hydride initiated polymerizationswhich features feeding one or more anionically polymerizable hydrocarbonmonomers to a reaction medium containing a soluble saline hydridecatalyst under an atmosphere comprising molecular hydrogen. Without suchfeatures the chemical process would otherwise produce either mainlyreduced monomer on one extreme or high molecular weight polymer at theother. In some embodiments of this invention the forgoing features actin concert and in balanced competition yielding anionic chain transferpolymer distributions with high yield, great efficiency and exceptionalcontrol of polymer chain length microstructure.

The present invention also relates to a process for anionic chaintransfer polymerization comprising feeding a vinyl aromatic monomerand/or preferably a styrenic monomer to a reaction mixture under anatmosphere comprising molecular hydrogen in a reactor vessel, whereinsaid reaction mixture was formed from (i) an organolithium compoundand/or an organomagnesium compound; (ii) optionally a polytertiaryaminecompound; (iii) a polarizing complexing agent selected from a tertiaryaminoalcohol compound; a tertiary amino ether-alcohol, an ether-alcoholor combinations thereof; (iv) optionally an alkali metal or metal alloyand/or a solid saline hydride and/or a saline metal amide; (v)optionally an aromatic hydrocarbon having at least one C—H covalent bondpK_(a) within the range of 2.75 pK_(a) units above that of the pK_(a) oftoluene to −4.30 pK_(a) units below the pK_(a) of toluene; (vi)optionally a vinylaromatic monomer; and in (vii) a hydrocarbon solventwith a pK_(a) greater than H₂; wherein the aromatic hydrocarbon andhydrocarbon solvent may be the same or different; (viii) optionallymolecular hydrogen; and wherein the solubility of hydride comprisingsaid catalyst or reagent is at least about 0.0080 moles per liter.

The present invention also relates to a process for anionic chaintransfer polymerization comprising feeding a vinyl aromatic monomerand/or preferably a styrenic monomer to a reaction mixture under anatmosphere comprising molecular hydrogen in a reactor vessel having ahydrogen mediated chain transfer polymerization catalyst of the formulas[DMEA⁻]_(x)Li_(y)H_(z), wherein said catalyst is formed from the processof contacting: (i) about y equivalents of an organolithium compoundand/or an organomagnesium compound; (ii) optionally TMEDA compound;(iii) about x equivalents of dimethylamionethanol; (iv) optionallyethylbenzene; (v) a hydrocarbon solvent with a pK_(a) greater than H₂;wherein the aromatic hydrocarbon and hydrocarbon solvent may be the sameor different; and (vi) molecular hydrogen, wherein the amount of hydrideformed z is given by the equation z=y−x and x, y and z are positive realnumbers whole or fractional greater than zero; wherein said formula canfurther comprise N,N,N′,N′-tetramethylethylenediamine (TMEDA) ligandcomplex i.e. [DMEA⁻]_(x)Li_(y)H_(z).XTMEDA in a molar ratio X of molesTMEDA per mole of catalyst [DMEA⁻]_(x)Li_(y)H_(z) wherein X=0.0001 toabout 8.0.

Thus, the present invention also relates to a process for anionic chaintransfer polymerization comprising: (a) feeding styrene monomer to;and/or (b) co-feeding styrene monomer with; a reaction mixture under anatmosphere comprising molecular hydrogen in a reactor vessel, whereinsaid reaction mixture was initially formed from (i) about y equivalentsof an organolithium compound; (ii) optionally TMEDA compound; (iii)about x equivalents of dimethylamionethanol; (iv) optionallyethylbenzene; and (v) a hydrocarbon solvent with a pK_(a) greater thanH₂; wherein the aromatic hydrocarbon and hydrocarbon solvent may be thesame or different; (vi) optionally molecular hydrogen; wherein ahydrocarbon soluble lithium hydride of the formulae[DMEA⁻]_(x)Li_(y)H_(z) is formed wherein the amount of hydride formed zis given by the equation z=y−x and x, y and z are positive real numberswhole or fractional greater than zero; and wherein the solubility ofhydride comprising said catalyst or reagent is at least about 0.0080moles per liter.

The present invention also relates to highly hydrocarbon solublebimetallic tertiary aminoalkoxide and/or tertiary amino ether-alkoxideand/or ether-alkoxide complexed lithium hydride and/or magnesium hydridecatalysts and/or reagents formed from a reaction medium comprising: (i)molecular hydrogen; (ii) an organolithium compound and/or anorganomagnesium compound; (iii) optionally a polytertiaryamine compound;(iv) a polarizing complexing agent selected from a tertiary aminoalcoholcompound; a tertiary amino ether-alcohol, an ether-alcohol orcombinations thereof; (v) optionally an alkali metal or metal alloyand/or a solid saline hydride and/or a saline metal amide; (vi)optionally an aromatic hydrocarbon having at least one C—H covalent bondpK_(a) within the range of 2.75 pK_(a) units above that of the pK_(a) oftoluene to −4.30 pK_(a) units below the pK_(a) of toluene; (vii)optionally a vinylaromatic monomer; and (viii) a hydrocarbon solventwith a pK_(a) greater than H₂; wherein the aromatic hydrocarbon andhydrocarbon solvent may be the same or different, and wherein thesolubility of hydride comprising said catalyst or reagent is at leastabout 0.0080 moles per liter.

The present invention also relates to highly hydrocarbon solublemonometallic tertiary aminoalkoxide and/or tertiary amino ether-alkoxideand/or ether-alkoxide complexed lithium hydride or lithium polyhydride(LiH_(n) where n=1+2x where x is a positive integer) complex and/oraggregate formed from a reaction medium comprising: (i) molecularhydrogen; (ii) an organolithium compound; (iii) optionally apolytertiaryamine compound; (iv) a polarizing complexing agent selectedfrom a tertiary aminoalcohol compound; a tertiary amino ether-alcohol,an ether-alcohol or combinations thereof; (v) optionally lithium metalor lithium alloy and/or a solid lithium hydride and/or a lithium amide;(vi) optionally an aromatic hydrocarbon having at least one C—H covalentbond pK_(a) within the range of 2.75 pK_(a) units above that of thepK_(a) of toluene to −4.30 pK_(a) units below the pK_(a) of toluene;(vii) a hydrocarbon solvent with a pK_(a) greater than H₂; wherein thearomatic hydrocarbon and hydrocarbon solvent may be the same ordifferent, and wherein the solubility of hydride comprising saidcatalyst or reagent is at least about 0.0080 moles per liter.

The present invention also relates to highly hydrocarbon soluble lithiumtertiary aminoalkoxide complexed lithium hydride (LiH) or lithiumpolyhydride (LiH_(n) where n=1+2x where x is a positive integer)hydrogen mediated chain transfer polymerization catalyst of the formulas[DMEA⁻]_(x)Li_(y)H_(z), wherein said catalyst is formed from the processof contacting: (i) about y equivalents of an organolithium compoundand/or an organomagnesium compound; (ii) optionally TMEDA compound;(iii) about x equivalents of dimethylamionethanol; (iv) optionallyethylbenzene; (v) a hydrocarbon solvent with a pK_(a) greater than H₂;wherein the aromatic hydrocarbon and hydrocarbon solvent may be the sameor different; and (vi) molecular hydrogen; wherein the amount of hydrideformed z is given by the equation z=y−x and x, y and z are positive realnumbers whole or fractional greater than zero; wherein said formula canfurther comprise N,N,N′,N′-tetramethylethylenediamine (TMEDA) ligandcomplex i.e. [DMEA⁻]_(x)Li_(y)H_(z).XTMEDA in a molar ratio X of molesTMEDA per mole of catalyst [DMEA⁻]_(x)Li_(y)H_(z) wherein X=0.0001 toabout 8.0.

The present invention also relates highly hydrocarbon soluble tertiaryaminoalkoxide and/or tertiary amino ether-alkoxide and/or ether-alkoxidecomplexed lithium deuteride (Li²H), or lithium tritide (Li³H) or lithiumpolydeuteride (Li²H_(n) where n=1+2x where x is a positive integer) orlithium polytritide (Li³H_(n) where n=1+2x where x is a positiveinteger) complex and/or formed from a reaction medium comprising: (i)isotopically enriched molecular hydrogen; (ii) an organolithium compoundand/or an organomagnesium compound; (iii) optionally a polytertiaryaminecompound; (iv) a polarizing complexing agent selected from a tertiaryaminoalcohol compound; a tertiary amino ether-alcohol, an ether-alcoholor combinations thereof; (v) optionally an alkali metal or metal alloyand/or a solid saline hydride and/or a saline metal amide; (vi)optionally an aromatic hydrocarbon having at least one C—H covalent bondpK_(a) within the range of 2.75 pK_(a) units above that of the pK_(a) oftoluene to −4.30 pK_(a) units below the pK_(a) of toluene; (vii)optionally a vinylaromatic monomer; and (viii) a hydrocarbon solventwith a pK_(a) greater than H₂; wherein the aromatic hydrocarbon andhydrocarbon solvent may be the same or different, and wherein thesolubility of hydride comprising said catalyst or reagent is at leastabout 0.0080 moles per liter.

The present invention further relates to highly hydrocarbon solublelithium tertiary aminoalkoxide complexed lithium hydride (LiH) orlithium polyhydride (LiH_(n) where n=1+2j where j is a positive integerincluding zero) complex and/or aggregates formed from a reaction mediumcomprising: (i) molecular hydrogen; (ii) about y equivalents of anorganolithium compound; (iii) optionally a TMEDA; (iv) about xequivalents of dimethylaminoethanol; (vi) optionally ethylbenzene; and(vii) a hydrocarbon solvent with a pK_(a) greater than H₂; wherein theethylbenzene and hydrocarbon solvent may be the same or different,wherein a hydrocarbon soluble lithium hydride of the formulae[DMEA⁻]_(x)Li_(y)H_(n) is formed wherein the amount of hydride formed zis given by the equation z=y−x and x, y and z are positive real wholenumbers greater than zero and n=z+2j; and wherein the solubility ofhydride comprising said catalyst or reagent is at least about 0.0080moles per liter.

This invention also relates to hydrogen mediated anionic polymerizationof styrene (HMAPS) processes which features: a) the novel ability ofsoluble lithium hydride species to rapidly polymerize styrene; b) thenovel high efficiency in which the addition of the lithium hydridespecies to styrene monomer takes place and thus allows the reinitiationstep to compete with the propagation reaction step to grow the activetransient living poly(styryl)lithium anionic chains thus maintaining aconstant or near constant number of active growing chains; c) thecapacity of chain transfer from hydrogen under mild and novel processconditions to terminate such living poly(styryl)lithium anionic speciesand regenerate the soluble lithium hydride in a form capable ofeffectively reinitiating the polymerization process; d) eliminates ornearly eliminates intramolecular chain transfer steps that otherwiselead to undesired quaternary carbon formation in the anionic polystyrenepolymer chains; and f) control of the MWD is accomplished via highrelative monomer to catalyst feed rates, catalyst concentration andhydrogen activity.

Thus the present invention also relates to an HMAPS process for anionicchain transfer polymerization comprising feeding styrene monomer to areaction mixture under an atmosphere comprising H₂ in a reactor vessel,wherein said reaction mixture contains a catalyst having the chemicalformulas [DMEA⁻]_(x)Li_(y)H_(z), wherein said catalyst is formed fromthe process of contacting: (i) about y equivalents of an organolithiumcompound and/or an organomagnesium compound; (ii) optionally TMEDAcompound; (iii) about x equivalents of dimethylamionethanol; (iv)optionally ethylbenzene; (v) a hydrocarbon solvent with a pK_(a) greaterthan H₂; wherein the aromatic hydrocarbon and hydrocarbon solvent may bethe same or different; and (vi) optionally molecular hydrogen; whereinthe amount of hydride formed z is given by the equation z=y−x and x, yand z are positive real numbers whole or fractional greater than zeroand wherein the solubility of hydride comprising said catalyst orreagent is at least about 0.0080 moles per liter.

The present invention also relates to saline hydride initiated anionicpolystyrene and anionic chain transfer polystyrene distributions inwhich the polystyrene chain length distribution of individual ordiscrete polymer chain constituents have the general formula:

wherein n is the number of repeating styrene monomer units covalentlybonded between the initiating styrene monomer and the terminatingstyrene monomer; wherein the chain length distribution of the generalformula above comprises at least about 97.0 wt. %, preferably at leastabout 98.0 wt. %, more preferably at least about 99.0% and mostpreferably comprises at least about 99.2 wt % of the total weight of thepolystyrene composition; and wherein the balance of the chain lengthdistribution is comprised of not more than 3.0 wt. %. or more preferablynot more than 2.0 wt. %, more preferably not more than 1.0%, and mostpreferably comprises not more than 0.8 wt % combined of: 1)distributions of polymer chains that are isomeric of 1; and/or 2)distributions formed from a chain fragmentation process step and thusare thereby essentially free of discrete chain length compositions withstructural formula weight (FW_(i)) given by the equation: FW_(i)=FW_(i)polystyrene ±14 Daltons.

The present invention further relates to lithium hydride initiatedanionic polystyrene and anionic chain transfer polystyrene distributionsin which the polystyrene chain length distribution of individual ordiscrete polymer chain constituents have the general formula 1: whereinn is the number of repeating styrene monomer units covalently bondedbetween the initiating styrene monomer and the terminating styrenemonomer; wherein the chain length distribution of the general formulaabove comprises at least about 99.0% and preferably comprises at leastabout 99.2 wt % of the total weight of the polystyrene composition; andwherein the balance of the chain length distribution is comprised of notmore than 1.0 wt. %. or more preferably not more than 0.8 wt % combinedof: 1) distributions of polymer chains that are isomeric of formula 1;and 2) are essentially free of chain length distributions formed from achain fragmentation-process step and thus have discrete chain lengthstructural formula weight (FW_(i)) where FW_(i)=FW_(i polystyrene)±14Daltons below a detection limit of about 0.02% by the GC Oligomer Test.

DETAILED DESCRIPTION OF THE INVENTION Glossary

It is to be understood and appreciated that the term “polymer” as usedanywhere herein, including the claims, refers to the term “polymer” asdefined in the context of the OECD definition of “polymer”, which is asfollows:

-   -   “A chemical substance consisting of molecules characterized by        the sequence of one or more types of monomer units and        comprising a simple weight majority of molecules containing at        least three monomer units which are covalently bound to at least        one other monomer unit or other reactant and which consists of        less than a simple weight majority of molecules of the same        molecular weight. Such molecules must be distributed over a        range of molecular weights wherein differences in the molecular        weight are primarily attributable to differences in the number        of monomer units.”

Saline Hydrides (meaning ionic hydrides) are defined by the presence ofhydrogen as a negatively charged ion, H⁻, in combination with an alkalimetal or alkaline earth metal: said alkali metals include lithium,sodium, potassium, rubidium, and cesium; and said alkaline earth metalsinclude magnesium and calcium.

Saline metal amide are metallic amides or diamides formed from ammoniaand/or a primary amine and/or a secondary amine wherein the metal ion incombination with the amide is an alkali metal selected from lithium,sodium, potassium, rubidium, and cesium; and in combination with thediamide is an alkaline earth and includes magnesium and calcium.

“Polymer microstructure” as used here refers to a discrete polymerchain's (or chain length distribution of such chains) configuration interms of its composition, sequence distribution, steric configuration,geometric and substitutional isomerism.

The term “head to tail” polymer microstructure is the description of themicrostructure exhibited by the styrene polymer structure (1) presentedabove. A head to tail microstructure exist when the head (being formedfrom the vinyl carbon bearing the phenyl substituent) of each styrenicmonomer unit is covalently bonded to the tail (being formed from thevinylidene carbon) of one and only one other styrenic monomer unit.

The term “tail to tail” microstructure exists when the tail of astyrenic monomer unit is covalently bonded to the tail of anotherstyrenic monomer unit. Such tail to tail microstructure is common aspart of the microstructure of anionic polymerizations of styrenicmonomers initiated by electron transfer mechanisms.

The term “tail to head to tail” microstructure means a polymer backbonelinkage where the head of one styrenic monomer is covalently bonded tothe tail of two other styrenic monomers. This microstructure produces anirregularity in the polymer backbone and incorporates an undesiredchemically labile (easily cleaved under certain reaction conditions)quaternary carbon in the polymer chain.

The terms “organolithium (active) alkyl”, “active” lithium and “activeorganolithium alkyl” (abbreviated as Li active) and the terms“organomagnesium (active) alkyl” and “active organomagnesium alkyl”means the total amount of either of these organometallic compounds asthe metal alkyl charged above the amount of organolithium and/ororganomagnesium compound needed to titrate any protic reagent as well asany protic impurity species such as water, and/or alcohol and/or aprimary or secondary amine. Though we wish not to be bound by theory itis considered to be that the molar amount of active organolithium isequal to the molar amount of saline hydride formed on a 1:1 basis. It isalso considered to be that one mole equivalent of active organomagnesiumcompound forms up to 2 equivalent moles of a saline hydride. For thispurpose the “active metal alkyl” represents lithium and/or magnesiumcovalently bonded alkyl radicals wherein the bonded alkyl radical can bean aliphatic, cycloaliphatic, aromatic, allylic, benzylic or vinylichydrocarbon radical.

Protic when in combination with the term species, or reagent, or solventor impurity means a chemical species having a covalently bonded proton(W) with a pK_(a) below that of H₂ under the conditions of the chemicalprocesses of this invention (see Buncel, E., Menon, B J. Am. Chem. Soc.,1977, 99, 4457: “Carbanion mechanisms. 6. Metalation of Arylmethanes byPotassium Hydride/18-Crown-6 Ether in Tetrahydrofuran and the Acidity ofHydrogen”).

“LOXSH” means a lithium aminoalkoxide or a lithium amine-ether-alkoxideor a lithium ether-alkoxide complexed saline hydride formed from: (i)molecular hydrogen; (ii) an organolithium compound with or without anorganomagnesium compound; (iii) optionally a polytertiaryamine compound;(iv) a tertiary amino alcohol and/or a tertiary amino ether-alcoholand/or a ether-alcohol; (v) an optional solid alkali or alkaline earthmetal hydride or an alkali metal or alkali metal alloy (vi) optionallyan aromatic hydrocarbon having at least one C—H covalent bond pK_(a)within the range of 2.75 pK_(a) units above that of the pK_(a) oftoluene to −4.30 pK_(a) units below the pK_(a) of toluene; and in (vii)a hydrocarbon solvent with a pK_(a) greater than H₂; wherein thearomatic hydrocarbon and hydrocarbon solvent may be the same ordifferent (see: Daasbjerg, K, Acta Chemica Scandinavica, 1995, 49, 878:“Estimation of the pK_(a) for some Hydrocarbons and Aldehydes andSolvantion Energies of the Corresponding Anions”).

LOXLiH is a term denoting the monometallic form of LOXSH where thecatalyst/reagent is formed with lithium reagents as the only metalreagents. LOXKH is term denoting a bimetallic catalyst comprised oflithium and potassium wherein a portion of the active saline hydride ispotassium hydride. LOXMgH₂ is term denoting a bimetallic catalystcomprised of lithium and magnesium wherein a portion of the activesaline hydride is a magnesium hydride.

[DMEA⁻]_(x)Li_(y)H_(z) represents chemical formulae for catalyst orreagent component compositions of hydrocarbon soluble lithiumaminoalkoxide complexed lithium hydride formed from: (i) molecularhydrogen; (ii) about y equivalents organolithium compound; (iii)optionally TMEDA; (iv) about x equivalents of dimethylaminoethanol; (v)optionally ethylbenzene; and in (vii) a hydrocarbon solvent with apK_(a) greater than H₂; wherein the hydrocarbon solvent may beethylbenzene or different (see: Daasbjerg, K, Acta Chemica Scandinavica,1995, 49, 878: “Estimation of the pK_(a) for some Hydrocarbons andAldehydes and Solvantion Energies of the Corresponding Anions”); whereinthe index values x, y and z are positive real numbers where theequivalents of hydride formed is z, wherein z=y−x and wherein for thestoichiometric ratio x:y:z; a) y is in the range of about 2 to about 6;b) x is in the range of about 1 to about 5; and thus z is in the rangeof about 5 to about 1. A preferred compositions of[DMEA⁻]_(x)Li_(y)H_(z) is a catalyst composition where thestoichiometric ratio x:y:z is 2:3:1 [DMEA⁻]₂Li₃H or where [DMEA⁻]₄Li₆H₂or [DMEA⁻]₆Li₉H₃ or any higher number multiple of x=2, y=3 and z=1.

The term “molecular hydrogen” means H₂ as ¹H₂ but can also include theisotopes of hydrogen ²H₂ or ³H₂ either as mixtures of the isotopes orenriched in a particular isotope whether in the gas state in the vaporspace or dissolved in the condensed phase.

The term “alkali metal alloy” means a metal alloy of at least two metalswherein at least one of which is an alkali metal however such an alkalimetal alloy can be comprised of two alkali metals such as NaK or NaK₂and may have such alkali metals dissolved or in some physicalcombination with the alloy.

The term “and/or” means singular or a combination. For example, “Aand/or B” means “A” alone, “B” alone, or a combination of A and B.

The term “with or without” means singular or in combination. For exampleA with or without B means “A” alone or a combination of A and B.

The terms “about x equivalents”, “about y equivalents” “about zequivalents” and the like mean±50%, or ±30% or ±20%, or ±10%, or ±5%from stoichiometric equivalents with the stipulation that the amount xis always less than the total amount of active y (i.e. “activeorganolithium reagent, a.k.a. active lithium) and thereby the amount zis a positive real number greater than but not equal to zero.

The term “organolithium compound” means an organic group bonded to alithium atom. Non-limiting examples of organic groups may be aliphatic(e.g., an alkyl group), cycloaliphatic (e.g., cycloalkyl), vinyl group,allylic group, benzylic group, an aromatic group (e.g., phenyl) or apoly(styryl)lithium.

The term “organomagnesium compound” means an organic group bonded to amagnesium atom. Non-limiting examples of organic groups may be aliphatic(e.g., an alkyl group), cycloaliphatic (e.g., cycloalkyl), vinyl group,allylic group, benzylic group, an aromatic group (e.g., phenyl) or apoly(styryl)magnesium. Preferred organomagnesium compounds areorganomagnesium compounds with two organic groups.

The “term polytertiaryamine (PTA) promotor” means a compound containingat least two tertiary amine groups that promotes or activates theformation of the hydride catalyst during the HMSHIP process.Non-limiting generic formulae would include:

where R′ and R″ are independently organic groups capable of formingbonds with two or more amines and R¹, R², R³, R⁴, and R⁵ areindependently organic groups which may also be further substituted byother tertiary amines, and the index value n is independently a wholenumber equal to or greater than 0 (i.e. n=0, 1, 2, 3 . . . ). It shouldbe understood that when n=0 than the group within the parentheses doesnot exist and the structure is intended to mean that the chemical bondis between the two groups that intersect the two sides of theparentheses. Thus polyteriary amine structure 2 becomes structure 4 whenn=0.

The term “polarizing complexing agent” is a general term for the neutralalcohol used in forming the catalyst of this invention such as atertiary amino alcohol, a tertiary amino ether-alcohol or aether-alcohol.

The terms “alkali or alkaline earth aminoalkoxide”, “alkali or alkalineearth amino ether-alkoxide” and “alkali or alkaline earthether-alkoxide” are alkoxides formed from the tertiary amino alcohol ora tertiary amino ether-alcohol or a ether-alcohol, respectively and analkali metal, and/or alkali or alkaline earth metal hydride, and/oralkali or alkaline earth metal amide or and/or alkali or alkaline earthmetal alkyl. The tertiary amino alcohols or tertiary aminoether-alcohols or a ether-alcohols can be represented by hut not limitedto the following generic, structures:

where R is an organic group capable of forming bonds with one or moretertiary amines and one hydroxyl, R¹ is independently an organic groupwhich may also be further substituted by other tertiary amines, Σ caninclude: i) O or NR¹ for 5, 6, 7, 8, 9 and 10; and ii) O or NR¹ or CH₂for 11; and the index value n is independently a whole number equal toor greater than 0 (i.e. n=0, 1, 2, 3 . . . ). It should be understoodthat when n=0 than the group within the parentheses does not exist andthe structure is intended to mean that the chemical bond is between thetwo groups or atoms that interconnect the two sides of the parentheses.Preferred aminoalcohols included dimethylaminoethanol,diethylaminoethanol, 3-Dimethylamino-1-propanol,N-methyl-deiethanolamine. tri-ethanolamine,2-[2-(dimethylamino)ethoxy]ethanol, 1-(2-hydroxyethyl)piperidine,1-(2-hydroxyethyl)morpholine, 1-(2-hydroxyethyl)pyrolidine,1-methyl-2-pyrolidinemethanol and the like.

It is preferred that the tertiary amino alcohols or tertiary aminoether-alcohols or ether-alcohols do not undergo additional metalationreactions other than the reaction to form the alkoxide. Thus not alltertiary amino alcohols or tertiary amino ether-alcohols orether-alcohols are suitable for use in forming some catalystcompositions, especially compositions formed with an excess amount ofcertain organolithium compounds—in particular alkyllithium reagents. Anexcess amount means a molar quantity greater than the molar quantity ofthe alcohol moiety of the tertiary amino alcohols or tertiary aminoether-alcohols or a ether-alcohols used to form the catalyst.Additionally the tertiary amino alkoxide or tertiary aminoether-alkoxide or ether-alkoxide should serve as solubilizing spectatorligand. That means that other than to function as activating polarizingcomplexing agent that imparts solubility to the saline hydride of thecatalyst composition and contributes to the activation and formation ofthe saline hydride during the HMSHIP process. Thus the polarizing ligandis otherwise inert and does not participate in the polymerizationprocess nor participate in catalyst degradation reactions. It isundesirable to incorporate the tertiary amino alcohols or tertiary aminoether-alcohols or ether-alcohols degradation products of such ligands orin the polymer structure or product distribution.

BRIEF DESCRIPTION OF THE DRAWINGS

1. FIG. 1 is drawing explaining the chemical reaction pathway leading toisomerization and further polymerization of a living (meaning ionized)anionic styrene trimer or styrene trimer equivalent (i.e. ethylbenzenecombined with two styrene monomers) to form and undesired quaternary“tail to head to tail” microstructure.

2. FIG. 2 is a drawing explaining the chemical reaction pathway thatentails fragmentation of an isomerized living (meaning ionized or as thepoly(styryl) anion or alkyl) anionic styrene trimer or styrene trimerequivalent with subsequent polymerization to form polymer chains havingformula weights given by the equations: FW_(i)=[i(104)+2−14] Daltons aswell as a discrete oligomer with FW_(i)=[i(104)+2+14] Daltons.

3. FIG. 3 is a gas chromatogram with structural assignments of thedesired high purity “head to tail” styrene oligomers obtained from a ofpolystyrene composition of this invention formed from a LOXLiH catalystof this invention employing a hydrogen mediated saline hydride initiatedpolymerization process of this invention.

4. FIG. 4 is a gas chromatogram of styrene oligomers obtained from apolystyrene composition of this invention formed from another LOXLiHcatalyst of this invention employing a hydrogen mediated saline hydrideinitiated polymerization process of this invention.

5. FIG. 5 is a gas chromatogram with structural assignments of styreneoligomers obtained from a polystyrene composition formed from a HASHcatalyst employing a hydrogen mediated saline hydride initiatedpolymerization process of this invention.

6. FIG. 6 is a gas chromatogram with structural assignments of styreneoligomers obtained from a polystyrene composition formed from a LOXKHcatalyst employing a hydrogen mediated saline hydride initiatedpolymerization process of this invention.

7. FIG. 7 is a gas chromatogram with structural assignments of styreneoligomers obtained from a polystyrene composition formed from a SASHcatalyst employing a hydrogen mediated saline hydride initiatedpolymerization process of this invention.

8. FIG. 8 is a gas chromatogram with structural assignments of the tracequantities of “head to tail” styrene oligomers initiated by unreducedbutylmagnesium as well as the high purity “head to tail” styreneoligomers obtained from a of polystyrene composition of this inventionformed from a LOXMgH₂ catalyst of this invention employing a hydrogenmediated saline hydride initiated polymerization process of thisinvention.

9. FIG. 9 is a gas chromatogram with structural assignments of acomparative ACTVAP composition of WO2008154453 formed fromn-propylbenzene and styrene under a nitrogen atmosphere provided as astandard for comparison. Standard for comparison: gas chromatogramdemonstrating oligomer microstructure purity for Comparative Example 44demonstrating the polymer microstructure of an Anionic Chain TransferVinyl Aromatic Polymer (ACTVAP) of WO2008154453 formed fromn-propylbenzene and styrene: 99.08% “Head to Tail” Microstructure

10. FIG. 10 is a gas chromatogram with structural assignments of acomparative ACTSP composition of WO2008154453 formed from toluene andstyrene under a nitrogen atmosphere provided as a standard forcomparison to identify the FW_(i)=[i(104)+2−14] (where i=2-6) Daltonsthat form from the undesired fragmentation polymerization process.Standard for comparison: gas chromatogram demonstrating oligomermicrostructure purity for an anionic chain transfer styrene polymer(ACTVSP) of WO2008154453 low molecular weight toluene styrene adducts;identical in structure to fragments (FW_(i)−14 where i=1 to 6)fragmentation oligomers formed in anionic styrene polymerizations thatemploy catalyst and/or initiators comprising potassium and/or sodiumions.

11. FIG. 11 is a gas chromatogram with structural assignments of acomparative mono-adduct of α-methylstyrene to ethylbenzene provided as astandard for comparison to identify the =[i(104)+2+14] (where i=2)Daltons that form from the undesired fragmentation polymerizationprocess that results in the in situ formation subsequent incorporationof α-methylstyrene. Standard for comparison: gas chromatogram of themono-addition product of α-methylstyrene to ethylbenzene identical instructure to the (FW_(i)+14) fragments specifically where i=1(210+14=224 MW oligomer) formed in anionic styrene polymerizationsemploying catalyst and/or initiators comprising potassium and/or sodiumions.

12. FIG. 12 is a gas chromatogram of oligomers obtained from theethylbenzene chain transfer polymerization of styrene process technologyof EPO 741147 demonstrating the undesired levels of polymermicrostructures arising from isomerization and fragmentationpolymerization reactions characteristic of the catalyst and processes ofthat technology.

13. FIG. 13 is a gas chromatogram of oligomers obtained from theethylbenzene (2 mole parts) chain transfer polymerization of styrene (1mole part) process technology of WO2008154453 demonstrating theundesired levels of polymer microstructures arising from isomerizationand fragmentation polymerization reactions characteristic of thecatalyst and processes of that technology when ethylbenzene is the chaintransfer agent.

14. FIG. 14 is a gas chromatogram of oligomers obtained from theethylbenzene (1 mole part) chain transfer polymerization of styrene (2mole parts) process technology of WO2008154453 demonstrating theundesired levels of polymer microstructures arising from isomerizationand fragmentation polymerization reactions characteristic of thecatalyst and processes of that technology when ethylbenzene is the chaintransfer agent.

15. FIG. 15 is a gas chromatogram of styrene oligomers obtained from apolystyrene composition of this invention formed from another LOXLiHcatalyst [DMEA⁻]_(x)Li_(y)H_(z).2TMEDA (wherein x:y:z is about 3:2:1) ofthis invention (Examples 52 and 53) employing a Hydrogen MediatedAnionic Styrene Polymerization (HMAPS) process of this inventionconducted at about 80° C. demonstrating 99.94% Head to Tailmicrostructure.

16. FIG. 16 is a gas chromatogram of styrene oligomers obtained from apolystyrene composition of this invention formed from another LOXLiHcatalyst [DMEA⁻]_(x)Li_(y)H_(z) (wherein x:y:z is about 3:2:1) of thisinvention (Examples 58 and 59) employing a Hydrogen Mediated AnionicStyrene Polymerization (HMAPS) process of this invention conducted atabout 80° C. demonstrating 99.97% Head to Tail microstructure.

17. FIG. 17 is a gas chromatogram of styrene oligomers obtained from apolystyrene composition of this invention formed from another LOXLiHcatalyst [DMEA⁻]_(x)Li_(y)H_(z) (wherein x:y:z is about 3:2:1) of thisinvention (Examples 64 and 65) employing a Hydrogen Mediated AnionicStyrene Polymerization (HMAPS) process of this invention conducted atabout 90° C. demonstrating 99.93% Head to Tail microstructure.

DESCRIPTION

The present invention relates a process of conducting hydrogen mediatedsaline hydride initiated polymerizations (HMSHIP) of anionicallypolymerizable hydrocarbon monomers, catalyst compositions for conductingsuch a process and under certain preferred conditions the formation ofnovel and beneficial low molecular weight anionic chain transfer polymerdistributions of very pure “head to tail” microstructure. The processfeatures feeding at least one anionically polymerizable hydrocarbonmonomer to a suitable solvent containing an active and generally solublesaline hydride catalyst under an atmosphere comprising molecularhydrogen wherein chain transfer from molecular hydrogen is a significantcomponent of the mechanism that determines the kinetic chain length (ν)distribution and hence the number average molecular weight (M_(n)) ofthe resulting product distribution.

One embodiment of the present invention relates to a process forhydrogen mediated anionic polymerization of vinyl aromatic monomers suchas styrenic monomers such as styrene using a hydrocarbon soluble LOXSHcatalyst. The hydrocarbon soluble LOXSH catalyst is formed from areaction medium comprising (i) an organolithium compound with or withoutan organomagnesium compound; (ii) an optional polytertiaryamine promotorcompound; (iii) a polarizing complexing agent selected from a tertiaryamino alcohol, a tertiary amino ether-alcohol an ether-alcohol orcombinations thereof; (iv) optionally an aromatic hydrocarbon having atleast one C—H covalent bond pK_(a) within the range of 2.75 pK_(a) unitsabove that of the pK_(a) of toluene to −4.30 pK_(a) units below thepK_(a) of toluene; (v) an optional solid alkali or alkaline earth metalhydride or an alkali metal or alkali metal alloy or a alkali or alkalineearth amide; (vi) a hydrocarbon solvent having a pK_(a) greater than H₂wherein the aromatic hydrocarbon and hydrocarbon solvent may be the sameor different; and (vii) molecular hydrogen. The product distributionformed from such a process when the monomer is solely styrenehereinafter designated LOXSH PS distribution. More specifically when thecatalyst is a monometallic catalyst comprised solely of lithium as themetal, that catalyst is designated as LOXLiH and the resulting anionicchain transfer styrene polymer distribution is a LOXLiH PS. However whenthe catalyst is bimetallic catalyst comprised of lithium and potassiumthat catalyst is designated as LOXKH and the resulting anionic chaintransfer styrene polymer distribution is a LOXKH PS. Likewise when thecatalyst is bimetallic catalyst comprised of lithium and magnesium thatcatalyst is designated as LOXMgH₂ and the resulting anionic chaintransfer styrene polymer distribution is a LOXMgH₂ PS.

In the practice of the invention the LOXSH catalyst can be optionallyformed in a variety of methods which are not limited by but include:

-   -   A. forming a well-mixed and reacted solution or suspension        comprised of (i), optionally (ii), (iii), optionally (iv) and        optionally (v) in (vi) under an inert atmosphere and then        converted to LOXSH by: 1) feeding a portion of the monomer to        the thus formed “ate” complex; and then 2) replacing or        otherwise displacing the inert atmosphere with H₂; or    -   B. forming a well-mixed and reacted solution or suspension        comprised of (i), optionally (ii), (iii), optionally (iv) and        optionally (v) in (vi) under an inert atmosphere to form a        precursor “ate” complex which is then converted to LOXSH by        replacing or otherwise displacing the inert atmosphere with        hydrogen; or    -   C. forming a well-mixed and reacted solution or suspension        comprised of a portion of (i) with optionally (ii), (iii), the        desired amount of (iv) and optionally (v) in (vi) in an external        reactor, transferring said solution to the polymerization        reactor under hydrogen and then charging the balance of (i); or    -   D. forming a well-mixed and reacted solution or suspension        comprised of optionally (ii), (iii), optionally (iv) and        optionally (v) in (vi) under a hydrogen atmosphere; feeding a        portion of the monomer then feeding (i) all at once; or    -   E. forming a well-mixed and reacted solution or suspension        comprised of optionally (ii), (iii), optionally (iv) and        optionally (v) in (vi) under a hydrogen atmosphere then        feeding (i) over a period greater than about 3 minutes then        optionally or when necessary feeding monomer; or    -   F. forming a well-mixed and reacted solution or suspension        comprised of (iii), optionally (iv) and optionally (v) in (vi)        under a hydrogen atmosphere then feeding (i) over a period        greater than about 3 minutes followed by the addition of desired        amount of (ii) then optionally or when necessary feeding        monomer.

It has been found that the LOXLiH and LOXMgH₂ catalyst/reagent isconveniently prepared in a very active and soluble form according tomethods E and F under a hydrogen atmosphere of 1.0 to 2.0 atmospheres H₂pressure though higher or lower H₂ pressures can be employed. Howeverthe LOXMgH₂ catalyst was not reduced to the hydride or at least was notcompletely reduced to the hydride by hydrogen until the monomer styrenewas introduced. Introduction of styrene forms a poly(styryl)magnesiumreagent that is completely reduced to the hydride during the hydrogenmediated chain transfer polymerization. Thus for the LOXMgH₂ may requirethe presence of a vinyl aromatic monomer in order to completely form thecatalyst in such cases feeding monomer is necessary and not optional.

The initial temperatures of about −5° C. to about 40° C. have beenemployed as set forth in the Examples below in forming the LOXLiH andLOXMgH₂ catalysts and or reagents of this invention. Lower or higherinitial temperatures can be used to form the catalyst especially whenusing an aminoalkoxide. Thus the organolithium (n-butyllithium) and orthe organomagnesium (di-n-butylmagnesisum) compound (i) is then fedslowly to the well stirred reaction mixture comprising dissolved H₂,(ii), (iii), in (vi) using a modest backpressure across a meteringneedle valve. Initially a heat kick ensues and the reactor pressure willrise if the organolithium and/or organomagnesium compounds produce lighthydrocarbons such as butane during the catalyst forming process.Subsequently the temperature has been observed to continue to risehowever the reactor pressure will generally drop below the initialpressure or remain constant as hydrogen is consumed in the catalystforming process. When the initial pressure is 0 PSIG then a negativepressure or slight vacuum is or can be created in the reactor. In mostcases, under the conditions set forth in the Examples the H₂ pressurewill usually drop during the feed of the organolithium reagent. Howeverin some Examples when temperatures below 15° C. and or when anorganomagnesium reagent is used, the reactor pressure does not appear todrop during the introduction of the organometallic reagent. Insteadreduction to the hydride occurs while warming the reaction mixture tothe desired reaction temperature. In the case of LOXMgH₂ catalyst,hydrogen uptake did not appear to be significant until the monomerstyrene was introduced at the reaction temperature of 70° C. or above.Mass Spec analyses of the lowest molecular weight oligomers obtainedfrom a LOXMgH₂ run demonstrated the presence of trace levels ofoligomers that had been initiated with a butyl group; this has not beenobserved in any of the other catalyst systems free of magnesium. Tofacilitate reduction of the LOXSH catalyst upon forming the catalystreaction mixture hydrogen is further charged to the reactor such thatthe reactor pressure will be from 40 to 70 PSIG once the reactionmixture has warmed to the desired initial polymerization reactiontemperature, though higher pressures can and have been employed.

In forming the catalyst compositions of this invention: LOXSH; LOXLiH;LOXMgH₂; or reagent producible by this invention hydrogen pressures from0.1 bar to greater than 300 bar can be used. The preferred H₂ pressureis in the range of from 0.25 bar to 10.00 bar and a more preferred rangeis from 0.5 bar to 7.0 bar and the most preferred range is from 0.75 barto about 5.0 bar. It has not escaped our attention that pressures ashigh as 100 G Pascals could in theory and perhaps in fact producepolyhydride compositions from the catalyst and reagents of thisinvention and hence the application of such pressures and formation ofsuch products are within the scope of this invention.

It is to be noted that commercially available organomagnesium compoundsmay contain about 0.12 to 0.25 wt % triethylaluminum (TEA) as anadditive to the reagent which is usually supplied in heptanes. Becausesuch organoaluminum reagents can have a retarding effect on anionicpolymerization reactions, it is desired that the ratio of lithium metalto aluminum metal be greater than 50.0:1.0 and preferably greater than101.0:1.0. As is depicted in FIG. 8 there was no evidence of initiationby or participation of TEA in the HMSHIP process of the LOXMgH₂ runsmade. Thus by analogy other organometallic reagents such asorganoaluminum, and or organoberyllium, and or organoboron agents can bepresent in the reaction mixture so long as the added reagent does notretard the HMSHIP process to the point that hydride addition to monomeris inhibited and/or that hydrogen chain transfer to the growing polymerchain is arrested or otherwise substantially interfered with andconsequently form a distribution of undesired molecular weightparameters.

Non-limiting preferred examples of organolithium compounds suitable forforming the LOXSH catalysts are n-butyllithium, sec-butyllithium,t-butyllithium, allyllithium, vinyllithium, phenyllithium,1-hexyl-1-phenyllithium, 1-hexyl-1,1-diphenyllithium, cyclohexyllithium,and poly(styryl)lithium compounds which can be added or generated insitu.

Non-limiting preferred examples of organomagnesium compounds suitablefor forming LOXMgH₂ catalysts are butylethylmagnesium (BEM),di-n-butylmagnesium (DBM), n-butyl-n-octylmagnesium,di-n-octylmagnesium, di-cyclohexylmagnesium, and poly(styryl)magnesiumcompounds. A comprehensive list of potential organomagnesium compoundsis provided in U.S. Pat. No. 3,817,955.

In forming a LOXMgH₂ catalyst it is possible to pre-form an “ate”complex having the stioichiometry R₃MgLi or R₄MgLi₂ where the group R isindependently an alkyl, vinyl, cycloalkyl, poly(styry), phenyl selectedfrom but not limited by any combination of the organolithium with anorganomagnesium recited above.

Non-limiting alkali or alkaline earth aminoalkoxide, alkali or alkalineearth amino ether-alkoxide and alkali or alkaline earth ether-alkoxide(designated as [PCA⁻]M or as [PCA⁻]₂M²⁺ for alkali and alkaline earthalkoxides respectively) formed in the process of forming a LOXSHcatalysts are formed from the generic structures of suitable polarizingcomplexing agents [PCAH] hereinabove. It should be clear that the[PCA⁻]M and/or as [PCA⁻]₂M²⁺ formed can be formed in situ when formingthe LOXSH catalysts and/or they can be formed well in advance andcharged to the catalyst forming reactor as the alkali or alkaline earthaminoalkoxide, alkali or alkaline earth amino ether-alkoxide and alkalior alkaline earth ether-alkoxide. Thus any alkali or alkaline earthreagent capable of forming either [PCA⁻]M and/or as [PCA⁻]₂M²⁺ from aPCAH and/or a [PCA⁻] precursor (e.g. an appropriate N,N-dialkylaminoacidsuitably reduced) can be employed in the practice of this invention andaccordingly is within the scope of this invention. As is demonstrated inExamples 25-27 the [PCA⁻] component of a catalyst composition can beformed in advance and subsequently charged during the catalyst formingreaction. Thus reagents such as solid alkali and alkali metal hydrides,alkali metal and alkali metal alloys, alkali metal and alkaline earthalkyls, alkali metal and/or alkaline earth amides (saline metal amides)can be used in the practice of this invention to react with a PCAHand/or a [PCA⁻] precursor to form the [PCA⁻] that comprises thecatalysts and reagents of this invention. Said formation of the [PCA⁻]M⁺and/or as [PCA⁻]₂M²⁺ can be conducted either; (a) in situ in thecatalyst forming reactor well in advance of catalyst formation and/orduring catalyst formation; and/or (b) in an external reactor associatedwith the catalyst forming reactor or completely separate from thecatalyst forming reactor. It should be noted however that use of asaline metal amide could potentially result in the incorporation of anamine functionality in the polymer compositions of this invention and insome applications is not desired. Additionally, the use of a complexedmetal hydride such as LiAH₄ to form a [PCA⁻]Li⁺ could require separationof the [PCA⁻]Li⁺ thus formed from the aluminum co-product of such areaction.

Examples 28 and 29 hereinafter demonstrate that the aminoether-alkoxides can under certain conditions degrade or decompose whenformed or during the course of a LOXLiH catalyzed HMSHIP process.Example 30 demonstrates that under certain process conditions the LOXLiHcatalyst formed from an ether-alkoxide formed from 2-methoxyethanol andan organolithium compound does not sufficiently activate the hydrogenchain transfer process. Thus the preferred polarizing complexing agentsespecially for a LOXLiH process are the aminoalkoxides. It is to beunderstood however that the amino ether-alkoxides may be well suited forLOXSH bimetallic catalyst low in LiH activity. Likewise conditions orprocesses where the LOXLiH catalyst formed from 2-methoxyethanol is moresuitable or more active can likely be found by through the practice ofthis invention.

There are many chiral tertiary aminoalcohols available that can besynthesized by reduction and further synthetic elaboration of chiralamino acids for example so a list of suitable aminoalcohols can beendless. Any advantage that the use of such chiral tertiary aminoalcohols may provide in terms of selectivity, tacticity or stereoregularity is well within the scope of this invention. Nonetheless, theless complex tertiary aminoalcohols which may be prepared by the simplereaction of an amine with reactive cyclic ethers such as ethylene oxideor other epoxides are preferred. Non-limiting examples of such tertiaryaminoalcohols that are readily available include: dimethylaminoethanol,diethylaminoethanol, N-methyl-diethanolamine,3-dimethylamino-1-propanol, 2-[2-(dimethylamino)ethoxy]ethanol,1-(2-hydroxyethyl)piperidine, 1-(2-hydroxyethyl)morpholine,1-(2-hydroxyethyl)pyrolidine, 1-methyl-2-pyrolidinemethanol and thelike.

Non-limiting examples of poly(tertiary amine) promotors useful in LOXSHcatalysts include di(tertiary amine) ligands derived from propylenediamine, di(tertiary amine) ligands derived from ethylene diamine orfrom polyethylene imine. Preferred examples includeN,N,N′,N′-tetramethylethylenediamine (TMEDA),N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA), sparteine,isosparteine, and 1,4-methylpiperazine wherein TMEDA is most preferred.The most preferred poly(tertiary amine) promotor ligands are the mostvolatile and/or the most water and/or acid soluble compounds thus TMEDAis preferred. The presence of the polytertiaryamine promotor compoundappears to facilitate formation of the LOXSH catalyst/reagent. A LOXSHprocess can be conducted in the absence of the polytertiaryaminepromotor however the presence of the polytertiaryamine promotor in someExamples provided LOXSH PS distributions of lower asymmetry and inincreased yields at reduced monomer feed rates and at reduced hydrogenpressure.

The preferred aromatic hydrocarbon which may be used is any aromatichydrocarbon having a pK_(a) relative to toluene ±2.75 pK_(a) unitshowever it is conceivable that an aromatic hydrocarbon such asdiphenylmethane with a pK_(a) of 4.32 units less than toluene can beemployed so long as: 1) the incorporation of diphenylmethane moiety inthe polymer microstructure does not affect the ultimate end use; and/or2) the pK_(a) of such hydrocarbons are sufficiently above that of H₂under the reaction conditions so as to not interfere with the hydrogenmediated chain transfer mechanism. Non-limiting examples of aromatichydrocarbons that may be used are benzene, toluene, mesitylene,ethylbenzene, n-propylbenzene, n-butylbenzene, iso-butylbenzne,amylbenzene, 1,2-diarylethanes, 1,3-diarylpropanes, cumene,t-butylbenzene, a 1-alkyl naphthalene, 2-alylnaphthalene or a styrenedimer or low molecular weight oligomer distribution (styrene dimers,trimers, tetramers and pentamers). Though the use of such aromatichydrocarbons is optional, their use is preferred in that it is believedtheir presence diminishes or preempts or otherwise mitigates theundesired attack of the organolithium more specifically an alkyllithiumreagent on the polytertiaryamine promotor. LOXSH catalysts can mitigateor inhibit the attack of the organolithium reagent on the alkali oralkaline earth aminoalkoxide, alkali or alkaline earth aminoether-alkoxide and “alkali or alkaline earth ether-alkoxide comprisingthe said catalyst. Hydrocarbons that are easily removed from the productdistribution by distillation or by polymer precipitation are preferred.The most preferred aromatic hydrocarbon for HMSHIP process utilizingstyrene is ethylbenzene.

The hydrocarbon solvent which may be used in any hydrocarbon having apK_(a) greater than molecular hydrogen (H₂) under the reactionconditions. Non-limiting examples of such preferred solvents arecyclohexane, methyl cyclohexane, and the aromatic hydrocarbons listedabove. Other hydrocarbon solvents can be used as long as their use doesnot affect the solubility of the saline hydride catalyst, reactiveintermediates, transient living polymer chains and the polymer chaindistribution product.

The aromatic hydrocarbon and the aromatic solvent may be the same ordifferent. This means that the aromatic hydrocarbon can act as both thearomatic hydrocarbon and the solvent. For example, ethylbenzene is apreferred component in the polymerization of styrene and can be used asboth the aromatic hydrocarbon and the solvent. In this case, for a LOXSHprocess components (iv) and (vi) would merge into one component (orlimitation) and be the same. Likewise, they can be different. Forexample, the aromatic hydrocarbon may be ethylbenzene and thehydrocarbon may be cyclohexane. Thus components (iv) and (vi) would bedifferent. Furthermore, component (iv) may be optional if no aromatichydrocarbon is used and, for example, cyclohexane is used as component(vi).

The partial pressure of hydrogen in the above LOXSH catalysts formingprocess is maintained at pressures between about 0.001 to about 10.0Bar, or about 0.3 to about 6.8 Bar, or about 0.5 to about 5.2 Bar orabout 1.0 to about 4.2 Bar.

In forming a monometallic LOXLiH catalyst from a tertiaryaminoalcoholand an organolithium compound the ratio of tertiaryaminoalcohol toorganolithium can vary widely. It should be understood however, in orderto form a lithium hydride species, a molar excess of the organolithiumcompound over the molar equivalent amount of tertiaryaminoalcohol mustbe used such that a lithium-carbon bond is available for reduction tothe lithium hydride species. It is conceivable to employ charge ratiosof 40 moles of tertiaryaminoalcohol per 41 moles of organolithiumreagent; however such charge ratios are a waste of expensive reagents.Preferred charge ratios (tertiaryaminoalcohol:organolithium) is in therange of from (1.00:1.05) to about (1:6), a more preferred range is from(1.00:1.10) to about (1:5); an even more preferred range is from(1.0:1.2) to about (1:4); and the most preferred range is from(1.00:1.40) to about (1:3).

Though we wish not to be bound by theory the results set forth in theExamples 33 and 34 below indicate that a (1:1.5)—i.e. (2:3) charge ratioof N,N-dimethylaminoethanol (DMEAH) to n-butyllithium with concurrent orsubsequent reduction with hydrogen to form the hydride provides adi-hydride catalyst with the formula [DMEA⁻]₄Li₆H₂ where only one of thetwo hydrides initiate polymerization of styrene under a cyclohexaneatmosphere. Similarly the Examples 35 and 36 indicate that a 1:2 ratioof DMEAH to n-butyllithium provides tetra-hydride catalyst with theformula [DMEA⁻]₄Li₈H₄ where only one of the four hydrides initiatepolymerization of styrene under a hydrogen atmosphere. Likewise a (1:3)charge ratio as used in Example 37) produced a soluble hydride catalystwith the formula [DMEA⁻]₂Li₆H₄ where only approximately 1 in 9 hydridesinitiated polymerization of styrene in a cyclohexane atmosphere. thusthis preferred catalyst composition in theory includes a mixture ofaggregates having the empirical formulae [DMEA⁻]₄Li₁₂H₈ in combinationwith [DMEA⁻]₅Li₁₅H₁₀ wherein both catalyst only one hydride is availablefor initiation of styrene polymerization in the absence of additionalmolecular hydrogen., A Most preferred catalyst composition is comprisedof catalyst aggregates having the overall empirical formula: (a)[DMEA⁻]₅Li₁₂H₇; and/or (b) [DMEA⁻]₂Li₅H₃ where the ratio of(tertiaryaminoalcohol:organolithium) is in the range of from (1:2.4) to(1:2.5). The same preferred ranges apply in forming soluble lithiumhydride complexes, catalyst and reagents from tertiary aminoether-alcohols and/or ether-alcohols.

It should be noted that it is believed that the LOXLiH catalyst whenformed under hydrogen exist as aggregates which under certainstoichiometry exist as well defined species of a fixed molecular weightwhile other stoichiometry or charge ratios provide catalyst that are notwell defined but exists as mixtures of non-uniform aggregates. It isfurther believed that the presence of a polytertiaryamine promotor canadditionally either stabilize certain aggregates or help to break upother less uniform mixtures of larger aggregates into smaller moreactive aggregates. Thus the activity of a catalyst system can varygreatly, but as a whole this class of catalyst is relatively poor atinitiation of living anionic polymerization. That is to say asinitiators the LOXLiH reagents in a H₂ free atmosphere are relativelyinefficient with regard to the availability of the hydride forinitiation (Eff_(CT)<1.0 and is in the range of Eff_(CT)=0.1 toEff_(CT)=0.67). Thus it remains extraordinarily surprising that thesesame catalyst so efficiently initiate and catalyze the hydrogen mediatedanionic chain transfer polymerizations of the present inventions withthe % Eff_(CT)=1000% to 16000% with the lower values—values closer to1000%—only resulting from intentional limiting use of the monomer.

The hydrocarbon soluble LOXSH catalyst may have the following empiricalchemical formulas: a) [PCA⁻]₄Li₆H₂, b) [PCA⁻]₄Li₈H₄; c) [PCA⁻]₂Li₆H₄; d)[PCA⁻]₄Li₁₂H₈; e) [PCA⁻]₅Li₁₅H₁₀; f) [PCA⁻]₅Li₁₂H₇; g) [PCA⁻]₂Li₅H₃; h)[PCA⁻]₄Li₄MgH₂, i) [PCA⁻]₄Li₄Mg₂H₄; j) [PCA⁻]₂Li₄MgH₄; k)[PCA⁻]₄Li₆Mg₃H₈; 1) [PCA⁻]₅Li₉Mg₃H₁₀; m) [PCA⁻]₅Li₆Mg₃H₇; n)[PCA⁻]₂Li₃MgH₃; o) [PCA⁻]₄Li₅KH₂; p) [PCA⁻]₄Li₇KH₄; and q)[PCA⁻]₂Li₅KH₄, and wherein said empirical formula can optionally furthercomprise a PTA promoter ligand complex in a molar ratio of total alkaliand alkali earth metal to PTA from about 10,000 to 1.0 to about 1.0 toabout 8.0. The preferred [PCA⁻] are [DMEA⁻], [DMAEOE⁻] or [MEOE⁻].

In forming the bimetallic Group I alkali metal LOXSH catalyst the ratioof tertiaryaminoalcohol to total alkali metal(tertiaryaminoalcohol:alkali) is in the range of range of from(1.00:1.05) to about (1:6), a more preferred range is from (1.00:1.10)to about (1:5); an even more preferred range is from (1.0:1.2) to about(1:4); and the most preferred range is from (1.00:1.40) to about (1:3).And the ratio of lithium to alkali metal excluding lithium (Li:Na and/orLi:K and/or Li:Cs etc.) is from (10,000:1) to (1:2), the preferred ratioare in the range of (34:1) to (2:1), and most preferred are (17:1) to(3:1). It is to be understood that in this connection a charge ratio of(10,000:1) can represent the unintended presence of alkali metal,potassium in particular, in even trace quantities due to an amount leftin the reactor or charge lines or tanks from previous runs where thealkali metal was intentionally charged. Potassium and other alkali metalbased bimetallic lithium catalysts have a tendency to deposit tracelevels of catalyst or catalyst by-products on reactor walls such tracelevels have been found to negatively impact the otherwise highlyselective microstructure delivered by a pure LOXLiH catalyst systemduring the hydrogen mediated saline hydride initiate polymerization ofstyrene.

Bimetallic lithium with sodium and/or with potassium and/or with cesiumbimetallic complex LOXSH catalyst with the empirical chemical formulae:a) [DMEA⁻]₄Na₄Li₄H₄; b) [DMEA⁻]₆Na₄Li₄H₂); c) [DMEA⁻]₆Na₄Li₆H₄; d)[DMEA⁻]₄K₄Li₄H₄; e) [DMEA⁻]₆K₄Li₄H₂); f) [DMEA⁻]₆K₄Li₆H₄; g)[DMEA⁻]₄Cs₄Li₄H₄; h) [DMEA⁻]₆Cs₄Li₄H₂); and i) [DMEA⁻]₆Cs₄Li₆H₄ areproducible from this invention. Additionally such bimetallic LOXSHcatalyst formulations in combination with the monometallic LOXLiHcatalyst formulations from above are within the scope of the invention.

In forming the magnesium hydride based bimetallic Group II alkalineearth complex with lithium, the LOXMgH₂ catalyst, the ratio of(tertiaryaminoalcohol:total-metal-equivalents) where lithium providesone equivalent and magnesium provides 2, is in the range from(1.00:1.05) to about (1:6), a more preferred range is from (1.00:1.10)to about (1:5); an even more preferred range is from (1.0:1.2) to about(1:4); and the most preferred range is from (1.00:1.40) to about (1:3).Thus a catalyst composition with the empirical formula [DMEA⁻]₄Li₄MgH₂(4 moles DMEAH to 5 total moles of metal is thus (4:6 or 1.0:1.5DMEAH:total-metal-equivalents) and is preferred. Likewise catalysts withthe empirical formulae: a) [DMEA⁻]₄Li₄Mg₂H₄ (1:2DMEAH:total-metal-equivalents); b) [DMEA⁻]₆Li₄Mg₂H₂ (1.00:1.33DMEAH:total-metal-equivalents); and c) [DMEA⁻]₆Li₄Mg₃H₄ (1.00:1.67DMEAH:total-metal-equivalents); alone or in combination with a LOXLiH orLOXSH catalyst formulation from above are within the scope of theinvention. The same preferred ranges in forming soluble bimetalliclithium magnesium hydride complexes, catalyst and reagents from tertiaryamino ether-alcohols and/or ether-alcohols can be used. The samepreferred ranges can be applied to form soluble bimetallic lithiumcalcium hydride complexes, catalyst and reagents fromtertiaryaminoalcohols and/or tertiary amino ether-alcohols and/orether-alcohols.

The invention further relates to a hydrocarbon soluble catalyst orreagent composition formed from reagents comprising a solid alkalihydride, an alkali metal and/or an alkali metal alloy wherein the ratioof polarizing complexing agent to total alkali metal is in the range ofrange of from about 1:1.05 to about 1:6; and the molar ratio oforganolithium compound to alkali metal is from 10,000:1 to 1:2.

Another embodiment is a hydrocarbon soluble monometallic LOXLiH catalystor reagent composition formed from molecular hydrogen and either:

-   -   a. a polarizing complexing agent reacted to a lithium alkoxide        and an organolithium compound wherein the molar ratio of        polarizing complexing agent to total alkali metal is in the        range of from about 1:1.05 to about 1:6; or    -   b. a polarizing complexing agent and an organolithium compound        wherein the molar ratio of polarizing complexing agent to total        alkali metal is in the range of from about 1:1.05 to about 1:6;        or    -   c. a polarizing complexing agent; at least one of solid lithium        hydride and/or lithium metal; and an organolithium compound        wherein the molar ratio of polarizing complexing agent to total        lithium is in the range of range of from about 1:1.05 to about        1:6.

Another embodiment is a hydrocarbon soluble catalyst or reagentcomposition comprising a magnesium hydride alkaline earth metal LOXMgH₂catalyst or reagent formed from molecular hydrogen and either:

-   -   a. a polarizing complexing agent reacted to form a lithium        and/or magnesium alkoxide; an organolithium compound and/or an        organomagnesium compound; wherein the molar ratio of polarizing        complexing agent to total-metal-equivalents is in the range of        from about 1:1.05 to about 1:6, where lithium provides one        equivalent and magnesium provides 2 equivalents; or    -   b. a polarizing complexing agent; an organolithium compound; and        an organomagnesium compound; wherein the molar ratio of        polarizing complexing agent to total-metal-equivalents is in the        range of from about 1:1.05 to about 1:6, where lithium provides        one equivalent and magnesium provides 2 equivalents; or    -   c. a polarizing complexing agent; at least one of solid lithium        hydride, metallic lithium, solid magnesium hydride; at least one        of an organolithium compound and/or an organomagnesium compound;        wherein the molar ratio of polarizing complexing agent to        total-metal-equivalents is in the range of from about 1:1.05 to        about 1:6, where lithium provides one equivalent and magnesium        provides 2 equivalents; or    -   d. a polarizing complexing agent; at least one of solid lithium        hydride and/or metallic lithium; and organomagnesium compound;        wherein the molar ratio of polarizing complexing agent to        total-metal-equivalents is in the range of from about 1:1.05 to        about 1:6, where lithium provides one equivalent and magnesium        provides 2 equivalents;    -   e. a polarizing complexing agent; solid magnesium hydride; and        an organolithium compound; wherein the molar ratio of polarizing        complexing agent to total-metal-equivalents is in the range of        from about 1:1.05 to about 1:6, where lithium provides one        equivalent and magnesium provides 2 equivalents.    -   f. and wherein the molar ratio of lithium to magnesium in the        catalyst composition is from 10,000:1 to 1:6.

Another embodiment is a process for forming a hydrocarbon solublecatalyst or reagent composition formed from: (i) molecular hydrogen;(ii) an organolithium compound and/or an organomagnesium compound; (iii)optionally a polytertiaryamine compound; (iv) a polarizing complexingagent selected from a tertiary aminoalcohol compound; a tertiary aminoether-alcohol, an ether-alcohol or combinations thereof; (v) optionallyan alkali metal or metal alloy and/or a solid saline hydride and/or aalkali amide; (vi) optionally an aromatic hydrocarbon having at leastone C—H covalent bond pK_(a) within the range of 2.75 pK_(a) units abovethat of the pK_(a) of toluene to −4.30 pK_(a) units below the pK_(a) oftoluene; and in (vii) a hydrocarbon solvent with a pK_(a) greater thanH₂; wherein the aromatic hydrocarbon and hydrocarbon solvent may be thesame or different.

In the above process, the hydrogen partial pressure used in forming thecatalyst or reagent is in the range of from about 0.1 bar to about 300bar. In addition, the temperature used in forming the catalyst orreagent is in the range of from about −96° C. to about 130° C.Furthermore, the molar equivalent charge ratios of the polarizingcomplexing agent to the organolithium compound and/or an organomagnesiumis in the range of from about 1:1.05 to about 1:6 moles of polarizingcomplexing agent per mole of metal-alkyl equivalents where lithiumprovides one equivalent and magnesium provides 2 equivalents. When PTAis used to form the catalyst or reagent, the molar ratios of the PTA tototal metal (magnesium and lithium) is from about 10,000:1.0 to about1:8.

One embodiment for forming the hydrocarbon soluble catalyst or reagentcomposition involves the steps of:

-   -   A. the polarizing complexing agent is first contacted with at        least one alkoxide forming reagent of: a) solid lithium        hydride; b) lithium metal; c) magnesium hydride; d) lithium        amide; e) magnesium amide; f) organolithium compound; g)        organomagnesium compound thereby forming a reaction mixture        wherein the stoichiometric molar equivalent ratio of polarizing        complexing agent to alkoxide forming reagent is from about 1:1        to less than 1:1 where lithium provides one equivalent and        magnesium provides 2 equivalents;    -   B. wherein the organolithium compound and/or organomagnesium        compound is further added;    -   C. wherein the ratio of polarizing complexing agent to total        metal equivalents is in the range of from about 1:1.05 to about        1:6 where lithium provides one equivalent and magnesium provides        2 equivalents;    -   D. wherein either the molar ratio of lithium to magnesium is in        the range of from about 10,000:1 to about 1.0:6.0;    -   E. and wherein the formed reaction product is further reduced        with hydrogen to form the hydrocarbon soluble saline hydride        catalyst or reagent.

Another embodiment for forming the hydrocarbon soluble catalyst orreagent composition involves the steps of:

-   -   A. the polarizing complexing agent is first contacted with an        alkali alkoxide forming reagent thereby forming a reaction        mixture wherein the stoichiometric molar equivalent ratio of        polarizing complexing agent to alkoxide forming reagent is from        about 1:1 to less than 1:1;    -   B. wherein said alkoxide forming reagent is at least one of a) a        solid alkali hydride; b) an alkali metal; c) an alkali metal        alloy; d) and alkali amide; e) magnesium amide; f) organolithium        compound; g) organomagnesium compound;    -   C. wherein the organolithium and/or organomagnesium compound is        further added;    -   D. wherein the ratio of polarizing complexing agent to total        alkali metal is in the range of from about 1:1.05 to about 1:6;    -   E. wherein either the molar ratio of lithium to non-lithium        alkali metal is in the range of range of from 1:2 to about        10,000:1 or the alkali metal of the catalyst composition is        exclusively lithium;    -   F. and wherein the formed reaction product is further reduced        with hydrogen to form the hydrocarbon soluble saline hydride        catalyst or reagent.

In the above process and steps for forming the hydrocarbon solublecatalyst or reagent composition, the process may further comprisesfeeding styrenic monomer to form a poly(styryl)magnesium and/or apoly(styryl)lithium compound prior to reduction by contacting withmolecular hydrogen to form the soluble saline hydride wherein the molarratio of styrenic monomer to total metal is from about 1:10 to about20:1. In another embodiment, the process may further comprises feedingstyrenic monomer to form a transient 1-phenyl-hexylmagneisium compoundand/or poly(styryl)magnesium compound which is further reduced bymolecular hydrogen to the soluble saline hydride wherein the molar ratioof styrenic monomer to magnesium is from about 1:5 to about 20:1 Thepreferred styrenic monomer is styrene.

In another embodiment of the present invention, a hydrocarbon solublecatalyst or reagent composition formed from: (i) molecular hydrogen;(ii) an organolithium compound and/or an organomagnesium compound; (iii)optionally a polytertiaryamine compound; (iv) a polarizing complexingagent selected from a tertiary aminoalcohol compound; a tertiary aminoether-alcohol, an ether-alcohol or combinations thereof; (v) optionallyan alkali metal or metal alloy and/or a solid saline hydride and/or aalkali amide; (vi) optionally an aromatic hydrocarbon having at leastone C—H covalent bond pK_(a) within the range of 2.75 pK_(a) units abovethat of the pK_(a) of toluene to −4.30 pK_(a) units below the pK_(a) oftoluene; (vii) a vinylaromatic monomer; and in (viii) a hydrocarbonsolvent with a pK_(a) greater than H₂; wherein the aromatic hydrocarbonand hydrocarbon solvent may be the same or different, and wherein thesolubility of hydride comprising said catalyst or reagent is at leastabout 0.0080 moles per liter.

Another embodiment of the present invention is a catalyst or reagentcomposition formed from: (i) molecular hydrogen; (ii) an organolithiumcompound and/or an organomagnesium compound; (iii) optionally apolytertiaryamine compound; (iv) a tertiary aminoalcohol compound and/ora tertiary amino ether-alcohol and/or a ether-alcohol; (v) optionally analkali metal or metal alloy and/or a solid saline hydride (vi)optionally an aromatic hydrocarbon having at least one C—H covalent bondpK_(a) within the range of 2.75 pK_(a) units above that of the pK_(a) oftoluene to −4.30 pK_(a) units below the pK_(a) of toluene; and in (vii)a hydrocarbon solvent with a pK_(a) greater than H₂; wherein thearomatic hydrocarbon and hydrocarbon solvent may be the same ordifferent.

A most desired LOXSH catalyst are the bimetallic LOXMgH₂ catalystcompositions or aggregates formed when the tertiary aminoalcohol isN,N-dimethylaminoalcohol (DMEAH) and depending on the reagent's chargeratios can have the empirical and/or molecular formulae as awell-defined composition or as the average composition of the catalystmixture in solution: a) [DMEA⁻]₄Li₄MgH₂, b) [DMEA⁻]₄Li₄Mg₂H₄; c)[DMEA⁻]₂Li₄MgH₄; d) [DMEA⁻]₄Li₆Mg₃H₈; e) [DMEA⁻]₅Li₉Mg₃H₁₀; (f)[DMEA⁻]₅Li₆Mg₃H₇; and (b) [DMEA⁻]₂Li₃MgH₃.

Among the most desired LOXSH catalyst are the monometallic LOXLiHcatalyst compositions or aggregates formed when the tertiaryaminoalcohol is N,N-dimethylaminoalcohol (DMEAH) and depending on thereagent's charge ratios can have the empirical and/or molecular formulaeas a well-defined composition or as the average composition of thecatalyst mixture in solution: a) [DMEA⁻]₄Li₆H₂, b) [DMEA⁻]₄Li₈H₄; c)[DMEA⁻]₂Li₆H₄; d) [DMEA⁻]₄Li₁₂H₈; e) [DMEA⁻]₅Li₁₅H₁₀; (f)[DMEA⁻]₅Li₁₂H₇; and (g) [DMEA⁻]₂Li₅H₃.

Thus preferred hydrocarbon soluble LOXLIH catalysts have the chemicalformulas [DMEA⁻]_(x)Li_(y)H_(z); wherein z=y−x and x, y and z arepositive real numbers, whole or fractional, greater than and not equalto zero and wherein said formula can optionally further comprise TMEDAligand complex in a molar ratio of total lithium to TMEDA from about10,000 to 1.0 to about 1.0 to about 8.0.

Thus this invention also relates to a hydrocarbon soluble catalyst orreagent composition formed from reagents comprising hydrogen, anorganolithium compound and dimethylaminoethanol and depending on thereagent's charge ratios can have the empirical and/or molecular formulaeas I) a well-defined LiH aggregate composition of 1)-105) in solution;or II) as the average LiH aggregate composition as any two or more of1)-105) in any proportion in solution; or III) one or more well-definedLiH aggregate composition or average composition in solution incombination with some insoluble LiH aggregate composition of 1)-105) outof solution; of one or more of the following

1) [DMEA⁻]Li₂H; 2) [DMEA⁻]₂Li₃H; 3) [DMEA⁻]Li₃H₂; 4) [DMEA⁻]Li₄H₃; 5)[DMEA⁻]₂Li₄H₂; 6) [DMEA⁻]₃Li₄H; 7) [DMEA⁻]Li₅H₄; 8) [DMEA⁻]₂Li₅H₃; 9)[DMEA⁻]₃Li₅H₂; 10) [DMEA⁻]₄Li₅H; 11) [DMEA⁻]Li₆H₅; 12) [DMEA⁻]₂Li₆H₄;13) [DMEA⁻]₃Li₆H₃; 14) [DMEA⁻]₄Li₆H₂; 15) [DMEA⁻]₅Li₆H; 16)[DMEA⁻]Li₇H₆; 17) [DMEA⁻]₂Li₇H₅; 18) [DMEA⁻]₃Li₇H₄; 19) [DMEA⁻]₄Li₇H₃;20) [DMEA⁻]₅Li₇H₂, 21) [DMEA⁻]₆Li₇H; 22) [DMEA⁻]Li₈H₇; 23)[DMEA⁻]₂Li₈H₆; 24) [DMEA⁻]₃Li₈H₅; 25) [DMEA⁻]₄Li₈H₄; 26) [DMEA⁻]₅Li₈H₃,27) [DMEA⁻]₆Li₈H₂; 28) [DMEA⁻]₇Li₈H; 29) [DMEA⁻]Li₉H₈; 30)[DMEA⁻]₂Li₉H₇; 31) [DMEA⁻]₃Li₉H₆; 32) [DMEA⁻]₄Li₉H₅; 33) [DMEA⁻]₅Li₉H₄,34) [DMEA⁻]₆Li₉H₃; 35) [DMEA⁻]₇Li₉H₂; 36) [DMEA⁻]₈Li₉H; 37)[DMEA⁻]Li₁₀H₉; 38) [DMEA⁻]₂Li₁₀H; 39) [DMEA⁻]₃Li₁₀H₇; 40)[DMEA⁻]₄Li₁₀H₆; 41) [DMEA⁻]₅Li₁₀H₅, 42) [DMEA⁻]₆Li₁₀H₄; 43)[DMEA⁻]₇Li₁₀H₃; 44) [DMEA⁻]₈Li₁₀H₂; 45) [DMEA⁻]₉Li₁₀H; 46)[DMEA⁻]Li₁₁H₁₀; 47) [DMEA⁻]₂Li₁₁H₉; 48) [DMEA⁻]₃Li₁₁H₈; 49)[DMEA⁻]₄Li₁₁H₇; 50) [DMEA⁻]₅Li₁₁H₆; 51) [DMEA⁻]₆Li₁₁H₅; 52)[DMEA⁻]₇Li₁₁H₄; 53) [DMEA⁻]₈Li₁₁H₃; 54) [DMEA⁻]₉Li₁₁H₂; 55)[DMEA⁻]₉Li₁₁H; 56) [DMEA⁻]Li₁₂H₁₁; 57) [DMEA⁻]₂Li₁₂H₁₀; 58)[DMEA⁻]₃Li₁₂H₉; 59) [DMEA⁻]₄Li₁₂H₈; 60) [DMEA⁻]₅Li₁₂H₇, 61)[DMEA⁻]₆Li₁₂H₆; 62) [DMEA⁻]₇Li₁₂H₅; 63) [DMEA⁻]₈Li₁₂H₄; 64)[DMEA⁻]₉Li₁₂H₃; 65) [DMEA⁻]₁₀Li₁₂H₂; 66) [DMEA⁻]₁₁Li₁₂H; 67)[DMEA⁻]Li₁₃H₁₂; 68) [DMEA⁻]₂Li₁₃H₁₁; 69) [DMEA⁻]₃Li₁₃H₁₀; 70)[DMEA⁻]₄Li₁₃H₉; 71) [DMEA⁻]₅Li₁₃H₇, 72) [DMEA⁻]₆Li₁₃H₇; 73)[DMEA⁻]₇Li₁₃H₆; 74) [DMEA⁻]₈Li₁₃H₅; 75) [DMEA⁻]₉Li₁₃H₄; 76)[DMEA⁻]₁₀Li₁₃H₃; 77) [DMEA⁻]₁₁Li₁₃H₂; 78) [DMEA⁻]₁₂Li₁₃H; 79)[DMEA⁻]Li₁₄H₁₃; 80) [DMEA⁻]₂Li₁₄H₁₂; 81) [DMEA⁻]₃Li₁₄H₁₁; 82)[DMEA⁻]₄Li₁₄H₁₀; 83) [DMEA⁻]₅Li₁₄H₉; 84) [DMEA⁻]₆Li₁₄H₈; 85)[DMEA⁻]₇Li₁₄H₇; 86) [DMEA⁻]₈Li₁₄H₆; 87) [DMEA⁻]₉Li₁₄H₅; 88)[DMEA⁻]₁₀Li₁₄H₄; 89) [DMEA⁻]₁₁Li₁₄H₃; 90) [DMEA⁻]₁₂Li₁₄H₂; 91)[DMEA⁻]₁₃Li₁₄H; 92) [DMEA⁻]Li₁₅H₁₄; 93) [DMEA⁻]₂Li₁₅H₁₃; 94)[DMEA⁻]₃Li₁₅H₁₂; 95) [DMEA⁻]₄Li₁₅H₁₁; 96) [DMEA⁻]₅Li₁₅H₁₀; 97)[DMEA⁻]₆Li₁₅H₉; 98) 9[DMEA⁻]₇Li₁₅E₁₈; 99) [DMEA⁻]₈Li₁₅H₇; 100)[DMEA⁻]₉Li₁₅H₆; 101) [DMEA⁻]₁₀Li₁₅H₅ 102) [DMEA⁻]₁₁Li₁₅H₄ 103)[DMEA⁻]₁₂Li₁₅H₃ 104) [DMEA⁻]₁₃Li₁₅H₂ 105) [DMEA⁻]₁₄Li₁₅Hor IV) any of I), II) or III) where the total composition of catalystaggregate can be expressed as [DMEA⁻]_(x)Li_(y)H_(z). Thus thehydrocarbon soluble [DMEA⁻]_(x)Li_(y)H_(z) catalysts of this inventionare formed from: (i) y equivalents of an organolithium compound; (ii) anoptional amount of TMEDA; (iii) x equivalents of dimethylaminoethanol;(iv) optionally ethylbenzenee; in (v) a hydrocarbon solvent having apK_(a) greater than H₂, wherein the aromatic hydrocarbon can beethylbenzene or different and (vi) molecular hydrogen, wherein theamount of hydride formed z is given by the equation z=y−x and x, y and zare positive real numbers whole or fractional greater than and not equalto zero

In the practice of the invention the [DMEA⁻]_(x)Li_(y)H_(z) catalystscan be optionally formed in a variety of methods which are not limitedby but include:

-   -   a) forming a well-mixed and reacted solution or suspension        comprised of about y equivalents of (i), optionally (ii), about        x equivalents (iii), optionally (iv) and in (v) under an inert        atmosphere and then converted to [DMEA⁻]_(x)Li_(y)H_(z) by: 1)        feeding a portion of the styrene to the thus formed “ate”        complex; and then 2) replacing or otherwise displacing the inert        atmosphere with H₂; or    -   b) forming a well-mixed and reacted solution or suspension        comprised of about y equivalents (i), optionally (ii), about x        equivalents of (iii), and optionally (iv) in (v) under an inert        atmosphere to form a precursor “ate” complex which is then        converted to [DMEA⁻]_(x)Li_(y)H_(z) by replacing or otherwise        displacing the inert atmosphere with hydrogen; or    -   c) forming a well-mixed and reacted solution or suspension        comprised of a portion of about x equivalents of (i) with        optionally (ii), about x equivalents of (iii), and        optionally (iv) in (vi) in an external reactor, transferring        said solution to the hydride forming reactor under hydrogen and        then charging the balance of about z or y-x equivalents (i); or    -   d) forming a well-mixed and reacted solution or suspension        comprised of optionally (ii), about x equivalents of (iii), and        optionally (iv) in (v) under a hydrogen atmosphere; then feeding        y equivalents of (i) all at once or in large proportion        increments; or    -   e) forming a well-mixed and reacted solution or suspension        comprised of optionally (ii), about x equivalents of (iii), and        optionally (iv) in (v) under a hydrogen atmosphere then feeding        about y equivalents of (i) continuously or in increments over a        period greater than about 3 minutes; or    -   f) forming a well-mixed and reacted solution or suspension        comprised of about x equivalents of (iii), and optionally (iv)        in (v) under a hydrogen atmosphere then feeding about y        equivalents of (i) continuously or in increments over a period        greater than about 3 minutes followed by the addition of desired        amount of (ii);    -   g) forming a well-mixed and reacted solution or suspension        comprised of x equivalents of (iii), and optionally (iv) in a        portion of (v) under a hydrogen atmosphere then feeding about y        equivalents of (i) previously further diluted with (iv) and/or a        portion of (v) continuously or in increments over a period        greater than about 3 minutes followed by the addition of desired        amount of (ii);    -   h) forming a well-mixed and reacted solution or suspension        comprised of about x equivalents of (i), and optionally (iv) in        a portion of (v) under a hydrogen atmosphere then feeding about        x equivalents of (iii) previously further diluted with (iv)        and/or a portion of (v) all at once, or continuously or in        increments over time until the entire charge of (iii) is        complete then feeding about z or y−x equivalents of (i) followed        by the addition of desired amount of (ii).

It has been found that the [DMEA⁻]_(x)Li_(y)H_(z) catalyst/reagent isconveniently prepared in a very active and soluble form according tomethods e), f), and g) under an initial hydrogen atmosphere of 1.0 to3.0 atmosphere H₂ pressure though higher or lower H₂ pressures can beemployed.

The initial temperatures of −96° to above 100° C. can be employed informing the [DMEA⁻]_(x)Li_(y)H_(z) catalysts and or reagents of thisinvention depending on the melting points of (iv) and (v) and thesolubilities and stabilities of (i), (ii) and (iii) under the reactionconditions. As set forth in the Examples, the [DMEA⁻]_(x)Li_(y)H_(z)catalyst were conveniently prepared at temperatures in the range of 35°to 40° C.

Thus when forming [DMEA⁻]₂Li₃H catalyst most typically about 3equivalents (y≈3) of organolithium compound (n-butyllithium 16.5 wt % incyclohexane) (i) further diluted with cyclohexane and ormethylcyclohexane (v) and/or ethylbenzene (iv) is then fed slowly (overa period of 15 to 25 minutes using a modest backpressure across ametering needle valve (20-30 PSIG back pressure drop across the valve)to the well stirred reaction mixture (about 50 to about 2000 RPMs;preferably about 200 to about 1500 RPMs; and most preferably about 500to about 1200 RPMs when using the pitched blade impellers describedherein below or any other suitable gas dispersing mixing apparatus) at35° C. to 40° C. comprising dissolved H₂ (15-22 PSIG H₂), about 2equivalents (x≈2) of dimethylaminoethanol (ii), in cyclohexane and ormethylcyclohexane (v) with or without ethylbenzene (iv). Initiallyduring the first ⅓ to about ⅔ of the feed of (i) a barely discernableheat kick ensues and the reactor pressure will increase 2-3 PSIG as aresult of the butane that is formed—i.e. when (i) is a butyllithiumreagent. The increase in reactor pressure is also in part the result ofthe compression of headspace vapors and gasses by the volume of the feedintroduced—especially when (i) is further diluted with large volumes of(iv) and/or (v). During the last about ⅓ of the feed of (i) thetemperature will rise (1.0° to 3.0° C. in the reactor described in theExamples) and the pressure will either stabilize or decrease by 1 to 3PSIG depending on the conditions used in forming the[DMEA⁻]_(x)Li_(y)H_(z) catalyst.

To facilitate complete reduction of the [DMEA⁻]_(x)Li_(y)H_(z) catalystupon forming the catalyst reaction mixture hydrogen is further chargedto the reactor such that the reactor pressure will be from 60 to 80 PSIGonce the reaction mixture has warmed to the desired initialpolymerization reaction temperature. It has been found though it is notnecessary to form an active catalyst, the most active forms of[DMSA⁻]_(x)Li_(y)H_(z) catalyst are prepared when this further charge ofhydrogen to elevated pressure is employed. It is also found that themost active and most reproducible catalyst are formed when the[DMEA⁻]_(x)Li_(y)H_(z) catalyst is held at the desired or near thehydrogen mediated anionic polymerization reaction temperature (about 68°to about 82° C.) for a period greater than about one hour, preferablygreater than about 2 to more than about 5 hours and then can be ventedto the desired H₂ pressure for the polymerization. It is not necessaryfor the practice of this invention to perform such catalyst agingprocedures; however the run to run reproducibility is more favored bythis technique. Though we wish not to be bound by theory, the catalystaging process may provide the highest concentration of available hydridein the form of well-defined catalyst compositions having 2, or 3 or 4LiH moieties within the discrete aggregate—depending on the charge ratioof (i):(iii). The catalyst aging process is considered as anequilibration or redistribution of initially formed higher aggregateshaving greater than 4 LiH moieties or equivalents per aggregate and orredistribution of catalyst aggregate compositions of less desired ratiosof x:y:z to form in higher concentration of catalyst aggregates ofdesired ratio of x:y:z.

Thus the most active catalysts have been formed when: (a) about 3equivalents of (i) (2.0 M in cyclohexane one part by weight) is furtherdissolved in ethylbenzene 8-10 parts by weight; (b) feeding (a) over aperiod of about 15 to 25 minutes to about 2 equivalents of (iii)dissolved in 24 to 28 parts by weight of (iv) and/or (v) free of (ii)stirred at about 500 RPMs at about 35° C. to 40° C. under a hydrogenatmosphere of 16 to 21 PSIG; (c) optionally adding (ii); (d) increasingthe hydrogen pressure to 50 PSIG and the mixing RPMS to 900 to about1200 RPMs; (e) warming the solution formed in (b) to about 65° to about85° C.; (f) further increasing the hydrogen pressure to about 75 PSIG;and (g) aging the catalyst for a period of about 1 hour to greater thanabout 5 hours. After the aging period the hydrogen pressure is carefullyvented from the reactor to the desired pressure for conducting thehydrogen mediated anionic polymerization of styrene processes of thisinvention. Hydrocarbon soluble lithium hydride compositions free of anycovalently bonded Lewis Acid group formed directly from hydrogen isheretofore unknown. Thus this equilibration or catalyst aging processunder hydrogen at elevated temperature is also a feature of thisinvention. This feature is not without some rational from the openliterature reports regarding formation of vicinal lithium aminoalkoxideaggregates as well as lithium aminoalkoxides complexed organolithiumreagents. Thus it has been reported that certain organolithium reagentsprepared from chiral vicinal lithium aminoalkoxides are made moreenantioselective towards the addition of the organolithium reagent toketones by following certain charge protocols and aging under cryogenicconditions the reagent components prior to introduction of the ketone.In this connection see: Collumn, D. B.; et. al. “Highly Enantioselective1,2 Addition of Lithium Acetylide-Ephedrate Complexes: SpectroscopicEvidence for Reaction Proceeding via 2:2 Tetramer, and X-rayCharacterization of Related Complexes”, J. Am. Chem. Soc. 2000, 122.11212.

Non-limiting preferred examples of organolithium compounds suitable forforming the LOXSH catalysts are n-butyllithium, sec-butyllithium,t-butyllithium, allyllithium, vinyllithium, phenyllithium,1-hexyl-1-phenyllithium, 1-hexyl-1,1-diphenyllithium, cyclohexyllithium,and poly(styryl)lithium compounds which can be added or generated insitu.

In forming a [DMEA⁻]_(x)Li_(y)H_(z) catalyst from a dimethylaminoethanoland an organolithium compound the ratio of dimethylaminoethanol toorganolithium can vary widely. It should be understood however, in orderto form a lithium hydride species a molar excess of the organolithiumcompound over the molar equivalent amount of dimethylaminoethanol mustbe used such that a lithium-carbon bond is available for reduction tothe lithium hydride species. It is conceivable to employ charge ratiosof 40 moles of dimethylaminoethanol per 41 moles of organolithiumreagent; however such charge ratios are a waste of expensive reagents.Preferred charge ratios (dimethylaminoethanol:organolithium) is in therange of from (1.00:1.05) to about (1:6), a more preferred range is from(1.00:1.10) to about (1:5); an even more preferred range is from(1.0:1.2) to about (1:4); and the most preferred range is from(1.00:1.40) to about (1:3). The [DMEA⁻]₄Li₆H₂ catalyst of the Exampleswere formed from a charge ratio of about 2 moles of dimethylaminoethanolto 3 moles of n-butyllithium.

It has been found that further dilution of about 2.0 molar or greatersolution of the organolithium reagent with the hydrocarbon solvent,especially with some portion of ethylbenzene to about ≤0.2 molar isbeneficial (but not necessary) in forming a more active[DMEA⁻]_(x)Li_(y)H_(z) catalyst. One explanation is that at lowerconcentrations of the organolithium compound is less likely to exist ina polymeric aggregate of organolithium species. The complicationsbrought on by the degree of association of alkyllithium compounds inliving anionic polymerization reactions of styrene and conjugated dienesis well established in the art (in this connection see Hsieh H. L. andQuirk, R. P. Anionic Polymerization Principles and PracticalApplications, Marcel Dekker, 1996, New York, pp 135-132 especially Table6.2 pg. 138). As normally supplied as relatively concentrated solutions(≥1.0 molar solutions) the degree of association of n-butyllithium isgenerally 6 wherein the degree of association of t-butyllithium andsec-butyllithium is generally 4 in hydrocarbon solvents. Dilution of theorganolithium compound with the solvent could result in reducedassociation of the organolithium reagents and thus a lower localizedorganolithium concentration when forming the [DMEA⁻]_(x)Li_(y)H_(z)catalyst. Though we wish not to be bound by theory, higher localconcentrations of the organolithium compound during catalyst formationcan result in the formation of less active—i.e. less availableLiH—superaggregates of the active [DMEA⁻]_(x)Li_(y)H_(z) catalyst. Thelower pK_(a) relative to aliphatic and cycloaliphatic hydro carbons maybe of some benefit as well in suppressing any undesired attack of theorganolithium reagent upon DMEAH beyond the initial formation of thelithium DMEA⁻ alkoxide. Thus it may be found that the use ofsec-butyllithium is more efficient than n-butyllithium due to theinherent lower state of association of this organolithium compound ascompared to n-butyllithium.

It should be noted that it is believed that the [DMEA⁻]_(x)Li_(y)H_(z)catalyst when formed under a hydrogen atmosphere exist as aggregateswhich under certain stoichiometry can exist as well defined species of afixed molecular weight while other stoichiometry or charge ratiosprovide catalyst that are not well defined but exists as mixtures ofnon-uniform aggregates or super aggregates. It is further believed thatthe presence of a polytertiaryamine promotor or any other suitableorganic Lewis base (e.g. tetrahydrofuran) can additionally eitherstabilize certain aggregates or help to break up other less uniformmixtures of larger aggregates into smaller more active aggregates. Thusthe activity of a catalyst system can vary greatly based on the chargeratios, catalyst components and the protocol followed in preparing thecatalyst.

The partial pressure of molecular hydrogen employed in forming the[DMEA⁻]_(x)Li_(y)H_(z) catalyst is maintained at pressures between about0.1 to about 300 Bar, or about 0.5 to about 12.0 bar, or about 1.0 toabout 10.0 Bar or about 1.1 to about 5.0 Bar. Low or high partialpressures of hydrogen can be employed so long as adequate mixing isprovided for mass transfer of H₂ from the vapor phase to the condensedphase thus mixing is critical in forming the [DMEA⁻]_(x)Li_(y)H_(z)catalyst in reasonably short periods of time.

The temperature employed in forming the [DMEA⁻]_(x)Li_(y)H_(z) catalystis maintained in the range of about −96° C. to about 130° C., morepreferably in the range of about 20° C. to about 110° C. and mostpreferred in the 30° C. to 90° C. In forming the [DMEA⁻]_(x)Li_(y)H_(z)catalyst and during a subsequent initial heat up, the catalystcomponents can be combined and reacted at the temperature just above themelting temperature of the hydrocarbon solvent (or mixture of solvents)or the freezing point of the monomer that is or will be fed. Combiningthe catalyst components at low temperatures (i.e. −10 to 15° C.) andeven under cryogenic conditions (−10° C. to −126° C.) may have thebenefit of avoiding or suppressing lithiation reactions that can lead topartial decomposition of the TMEDA promotor and/or DMEAH used.

In that nitrogen may (though no evidence of this has been observed)potentially be “fixed” by—that is N₂ may be reduced by—the[DMEA⁻]_(x)Li_(y)H_(z) catalyst of this invention it is potentiallydesirable but perhaps not necessary to eliminate or at least minimize N₂from the reactor headspace and system. It is possible to operate withother gases present which are generally deemed inert toward activatedhydrides such as a noble gas (He, Ne, Ar) or a relatively lightaliphatic or cycloaliphatic hydrocarbon (hydrocarbon with boiling pointclose to or less than the reaction temperature).

Of these inert gases the relatively light hydrocarbons are preferred(including any C4 hydrocarbons formed from a butyllithium reagent)because such hydrocarbons are generally soluble in the reaction mediumand hence do not displace H₂ with decreasing head space volume andthereby or reduce the partial pressure of H₂ in significantly varyingamounts during the course of the monomer feed at a constant reactorpressure. Thus inert gases that become compressed in the head space asthe condensed phase volume increases are less desired. However thepresence of such low solubility gases such as the noble gases in acontinuous process where the headspace volume is fixed may perhaps beused to some benefit. It is difficult to operate a commercial reactor atlow positive pressures of constant pressure thus it may be advantageousto have present low boiling (petroleum ethers) hydrocarbons such that adesired H₂ partial pressure and hence activity can be maintained at ahigher overall reactor pressure. Such light hydrocarbons can evenprovide the added benefit of some means of refluxive cooling.

When forming the [DMEA⁻]_(x)Li_(y)H_(z) catalyst TMEDA can optionally bepresent during the reduction or hydride forming process or be optionallyadded subsequent to hydride formation. TMEDA may facilitate formation orthe [DMEA⁻]_(x)Li_(y)H_(z) catalyst under certain conditions or it maybe beneficial in promoting the [DMEA⁻]_(x)Li_(y)H_(z) catalyst activityduring its use but it is not necessary for forming the catalyst. In factthere is some evidence that the presence of even trace amounts of TMEDAduring catalyst formation can lead to diminished catalyst activity. Itis presumed that TMEDA complexed organolithium reagents can undergocompetitive reduction to form Schleyer's super active nanometric sizedLiH (Schleyer, P. v. R.; et. al. J. Org. Chem. 1987. 52, 4299; andSchleyer, P. v. R.; et. al. Angew Chem Int. Ed. Engl. 198625465). Suchnanometric LiH has been to be found to be very ineffective as a catalystfor HMAPS processes (described below) and thus its co-formation wouldreduce the titer of active catalyst. Thus it is recommended though notcompletely necessary to add TMEDA after formation of the[DMEA⁻]_(x)Li_(y)H_(z) catalyst. Likewise it is recommended that someeffort is taken at reducing if not eliminating adventitious TMEDA fromthe [DMEA⁻]_(x)Li_(y)H_(z) catalyst forming steps by means of rinsingthe catalyst forming reactor and reactor train prior to use as well asacid extraction or removal of TMEDA from recycle solvents. It is evenadvisable but not necessary to form the [DMEA⁻]_(x)Li_(y)H_(z) catalystin a reactor, transfer the catalyst to the HMAPS polymerization reactoralready charged with or to be charged with TMEDA.

When employing a TMEDA, it is present in a molar ratio of lithium toTMEDA (lithium:TMEDA), in a ratio of from about the limit of (∞:1) ormore practically (10,000:1) to about (1:8), or preferably about (5:1) orabout (1:5) or even more preferably (3:1) to about (1:3). It is to beunderstood that in this connection a charge ratio of (∞:1) or morepractically (10,000:1) can represent the unintended presence of theTMEDA promotor in even trace quantities due to an amount left in thereactor or charge lines or tanks from previous runs where the TMEDA wasintentionally charged. Further it is within the scope to have a chargeratio greater than (1:8) total lithium to TMEDA, however such a chargeratio provides little if any advantage and represents and uneconomic useof the TMEDA promotor as well as any reagent and/or added effort neededto remove and/or recover the TMEDA promotor from the reaction or productmixture.

The hydrocarbon solvent which may be used in forming the LOXLiH[DMEA⁻]_(x)Li_(y)H_(z) catalyst is any hydrocarbon having a pK_(a)greater than molecular hydrogen (H₂) under the reaction conditions.Non-limiting examples of such preferred solvents are cyclohexane,methylcyclohexane, used with or without ethylbenzene. Other hydrocarbonsolvents may be used as long as their use does not affect: 1) thesolubility of the saline hydride catalyst, reactive intermediates,transient living polymer chains and the polymer chain distributionproduct; or 2) when using the catalyst for an HMSHIP or HMAPS process,the solvent does not act as an organic chain transfer agent ofsufficient activity that the hydrocarbon solvent is incorporated in theHMAPS product distribution at a level of about 2 wt % or more.

Further Detailed Description of this Invention

Another embodiment of the present application relates to a process forhydrogen mediated anionic chain transfer polymerization comprisingfeeding an anionically polymerizable monomer such as a vinyl aromatic,and/or a styrenic monomer under an atmosphere comprising molecularhydrogen to a reactor vessel containing a reaction mixture of ahydrocarbon solvent and a hydrocarbon soluble saline hydride catalyst.The soluble saline hydride catalyst includes a LOXSH catalyst eitherused separately or in combination. Preferred embodiments of the LOXSHcatalyst process have kinetic chain length distributions (ν), hencedegree of polymerizations (DP_(n)) and hence number average molecularweights (M_(n)) that are determined or otherwise set by the followingrelationship:

$\psi^{- 1} = {C_{{tr}_{H_{2}}}\frac{\left\lbrack H_{2} \right\rbrack}{\lbrack{sty}\rbrack}}$

thus M_(n) is essentially set exclusive of other kinetic terms and thusthe polymers are essentially anionic chain transfer polymerdistributions formed exclusively from hydrogen and monomer without anysignificant incorporation—at least less than about 2 wt %, morepreferably less than 1 wt % and more preferably less than 0.1 wt %—ofany added organic chain transfer agent. Thus the M_(n) of such polymers(excluding of ethylbenzene content) when the monomer is styrene is givenby:

$M_{n} \approx {\left( {\frac{{moles}\mspace{14mu}{styrene}}{{moles}\mspace{14mu}{Hydrogen}}*104} \right) + 2}$

wherein the moles of styrene is the amount of styrene fed, the moles ofhydrogen consumed and wherein the moles of ethylbenzene produced issmall preferably less than 10 wt %, more preferably less than 7 wt % andmost preferably less than 5 wt % of the product composition.

Thus the present invention also relates to a LOXSH catalyst process foranionic chain transfer polymerization comprising feeding an anionicallypolymerizable monomer (e.g. vinyl aromatic monomers and/or preferably astyrenic monomers) to a reaction mixture under an atmosphere comprisingmolecular hydrogen in a reactor vessel, wherein said reaction mixturewas formed from (i) an organolithium compound and/or an organomagnesiumcompound; (ii) optionally a polytertiaryamine compound; (iii) apolarizing complexing agent selected from a tertiary aminoalcoholcompound; a tertiary amino ether-alcohol, an ether-alcohol orcombinations thereof; (iv) optionally an alkali metal or metal alloyand/or a solid saline hydride and/or a saline metal amide; (v)optionally an aromatic hydrocarbon having at least one C—H covalent bondpK_(a) within the range of 2.75 pK_(a) units above that of the pK_(a) oftoluene to −4.30 pK_(a) units below the pK_(a) of toluene; (vi)optionally a vinyl aromatic monomer; and (vii) a hydrocarbon solventwith a pK_(a) greater than H₂; wherein the aromatic hydrocarbon andhydrocarbon solvent may be the same or different; (viii) molecularhydrogen; and wherein the solubility of hydride comprising said catalystor reagent is at least about 0.0080 moles per liter.

The same non-limiting examples and amounts of the components listedabove for forming the LOXSH catalyst as well as used in the abovecatalytic and or reagent compositions may be used for conducting theLOXSH catalyst saline hydride initiated hydrogen mediated polymerizationprocesses and need not be repeated.

The hydrocarbon and aromatic hydrocarbon solvent may be the same ordifferent. This means that the aromatic hydrocarbon can act as both thearomatic hydrocarbon and the solvent. Ethylbenzene is a preferredcomponent in a commercial hydrogen mediated anionic polymerization ofstyrene given that a portion of the styrene is reduced to ethylbenzeneand thus ethylbenzene is a likely component of recycled solvent unlessgreat care, time and energy is taken in the fractional distillation ofthe co-product ethylbenzene from the hydrocarbon solvent used in formingthe LOXSH catalyst as well as to conduct the LOXSH process of thisinvention. It is conceivable to use exclusively ethylbenzene and in thiscase, for LOXSH catalyst forming process components (v) and (vii) wouldmerge into one component (or limitation) and be the same. It is alsoconceivable to use an ethylbenzene free process using ethylbenzene freerecycle and/or fresh hydrocarbon solvents.

The anionically polymerizable hydrocarbon monomers can include one ormore vinyl aromatic monomers, especially styrenic monomers. Preferably,the vinyl aromatic monomer is a styrenic monomer such as styrene, oralkylated styrene monomers such as the o- m-, and p-, isomers of methylstyrene, p-isopropylstyrene, 2,4-diethylstyrene, o-ethylstyrene,3,5-di-isobutylstyrene, 2,6-dimethyl styrene, 2-ethyl-4-methyl styreneand combinations thereof. For forming linear polymeric microstructuresfree of branching molecular architectures, styrene is the preferredvinyl aromatic monomer. Alkylated styrene monomers under certain processconditions will themselves behave as chain transfer agents and result insome degree of branching and potential cross linking. Divinyl aromaticmonomers such as divinylbenzene can also be used as co-monomers howeverbranching and crosslinking can occur. Styrenic monomers such as alphaalkylated styrenes (e.g. α-methylstyrene) generally do nothomopolymerize under chain transfer conditions but can be used asco-monomers especially with conjugated dienes. However it should benoted that the use of an alpha alkylated styrene will result information of quaternary carbons in the polymer microstructure. Thus theuse of such alpha alkylated styrenes should be avoided for styrenicpolymers formed as substrates for derivatization by electrophilicaromatic substation reactions.

The partial pressure of molecular hydrogen employed in the above LOXSHcatalyst process is maintained at pressures between about 0.5 to about19.0 Bar, or about 1.5 to about 12.0 bar, or about 2.5 to about 10.0 Baror about 3.0 to about 7.0 Bar.

A hydrogen partial pressure greater than about about 10.0 Bar ispermissible for a period of time during the process when processconditions entail routine operation with adequate mixing to maintainhydrogen transfer to the condensed phase. However a substantial amountof time at such increased hydrogen partial pressures will generallyresult in hydrogenation of the monomer with a substantial reduction ofpolymer molecular weight. Conversely, hydrogen pressures below 0.1 Bar(less than 1.5 PSI) are permissible during routine operation of theprocesses involving potassium hydride forms of the LOXKH catalysts.Under such conditions of low hydrogen partial pressure and hence low H₂activity in the condensed phase, chain transfer from the organic chaintransfer agents whether added or formed during the course of the runwill compete more substantially. When employing a LOXLiH, or a LOXMgH₂and combinations thereof, feeding monomer for short periods of timeunder conditions of poor hydrogen mass transfer results in theproduction of a high molecular weight polymer chains and consequently amore asymmetric product distribution with a high molecular weight tail(as reflected by a substantial increase in the GPC measured value “M_(w)10% High” in Daltons). It is pointed out that the partial pressuresrecited above are only meaningful if adequate mass transfer of molecularhydrogen to the condensed phase is maintained such that the partialpressure reflects the condensed phase activity of molecularhydrogen—i.e. a steady state mass transfer of H₂ to the condensed phaseis established. Thus much higher H₂ partial pressures can be appliedwhen mass transfer to the condensed phase is diminished due to poormixing of the vapor phase with the condensed phase and thus results inpoor mass transfer.

In that nitrogen may (though no evidence of this has been observed)potentially be “fixed” by—that is N₂ may be reduced by—the salinehydride catalyst of this invention and because as the reactor headspacevolume is reduced by the monomer feed when operating under semi-batchconditions, it is potentially desirable but perhaps not necessary toeliminate or at least minimize N₂ from the reactor headspace and system.It is possible to operate with other gases present which are generallydeemed inert toward activated hydrides such as a noble gas (He, Ne, Ar)or a relatively light aliphatic or cycloaliphatic hydrocarbon(hydrocarbon with boiling point close to or less than the reactiontemperature). Of these inert gases the relatively light hydrocarbons arepreferred because such hydrocarbons are generally soluble in thereaction medium and hence do not displace H₂ and thereby do not reducethe partial pressure of H₂ in significantly varying amounts during thecourse of the monomer feed at a constant reactor pressure. Thus inertgases that become compressed in the head space as the condensed phasevolume increases are less desired. However the presence of such lowsolubility gases such as the noble gases in a continuous process wherethe headspace volume is fixed may perhaps be used to some benefit. It isdifficult to operate a commercial reactor at low positive pressures ofconstant pressure thus it may be advantageous to have present lowboiling (e.g. petroleum ethers) hydrocarbons such that a desired H₂partial pressure and hence activity can be maintained at a higheroverall reactor pressure. Such light hydrocarbons can even provide theadded benefit of some means of refluxive cooling.

The temperature of the reaction mixture and/or process is maintained inthe range of about 20° C. to about 130° C., more preferably in the rangeof about 40° C. to about 110° C. and most preferred in the range ofabout 60° C. to about 90° C.

The molar ratio of the total charge of monomer to metal hydride compoundinitially formed, (monomer:metal hydride), is about (10:1) to about(1000:1), or about (10:1) to about (600:1) or about (40:1) to about(600:1), or about (150:1) to about (360:1). Whereas the molar quantityof metal hydride formed is taken as being equal to the molar quantity oforganometallic bonds—organolithium and/or organomagnesium carbon-metalbonds, the conjugate acid thereof having a pK_(a)>H₂—that remain afterreaction with all protic species having a pK_(a)<H₂ under the conditionsof the catalyst forming reactions. Any decrease in the amount of metalhydride due to decomposition reactions is not taken into account andconditions (e.g. temperatures) as well as reagents (e.g. organic speciessuch as certain ethers that easily undergo metalation and decompositionby organolithium reagents) that contribute to catalyst deactivation ofsimply best avoided.

In the batch or semi-batch operation of the process technology of thisinvention the monomer (e.g. styrene) is fed with time to the reactionmedium, hence the initial ratio monomer to saline metal hydride formedat the very instant that the vapor from the first drop or increment ofmonomer fed is mathematically approaches the limit (1:∞). Thus a totalmonomer charged to the initially formed saline metal hydride molar ratiooutside the preferred recited ranges—i.e. a molar ratio in the range offrom the limit of (1.00:∞ to 1.00:0.101) which is about (1:10,000 toabout 9.9:1.0) monomer to saline metal hydride formed—are demonstratedas workable ranges at the outset of each of the Examples provided below.However the monomer feed is generally continued until the higher desiredmonomer to metal hydride ratio is complete. The practice of a chargemolar ratio limited to (1:10,000 to about 9.9:1.0) is within the scopeof the invention but simply represent uneconomical utilization of theorganolithium compound and/or organomagnesium compound.

Conversely feeding monomer at a relative molar ratio to saline metalhydride compound initially greater than about 1000:1 becomes unworkable;resulting in diminished chain transfer producing compositions ofundesired molecular weight distributions (MWD). The LOXLiH catalyzedprocess is a more preferred process both because of ease in forming thecatalyst, selectivity with regard to microstructure and finally becauseof catalyst activity. In Examples 14 and 15 it is demonstrated that ancatalyst efficiency of 15,000% can be achieved using a >600:1monomer:metal hydride charge ratio. The combination of these two runsproduced a dimer stripped polymer distribution characterized as havingM_(w)=730 with PD_(n)=1.4 in 75% isolated yield.

For the LOXSH process, the polytertiaryamine (PTA) promotor is optional.Accordingly, when employing a monomeric PTA composition, the PTApromotors is present in a molar ratio of total alkali and alkali earthmetal to PTA (metal:PTA), in a ratio of from about the limit of (∞:1) ormore practically (10,000:1) to about (1:8), or preferably about (5:1) orabout (1:5) or even more preferably (3:1) to about (1:3). It is to beunderstood that in this connection a charge ratio of (1: ∞) or morepractically (10,000:1) can represent the unintended presence of the PTApromoter in even trace quantities due to an amount left in the reactoror charge lines or tanks from previous runs where the PTA wasintentionally charged. Further it is within the scope to have a chargeratio greater than (1:8) total metal to PTA, however such a charge ratioprovides little if any advantage and represents and uneconomic use ofthe PTA promotor as well as any reagent and/or added effort needed toremove and/or recover the PTA promotor from the reaction or productmixture.

The monomer feed rates relative to the amount of catalyst is among thedetermining kinetic factors with regard to setting the polymercomposition's polydispersity, PD_(n), and hence the overall molecularweight distribution (MWD) as measured by the values of M_(n), M_(w),M_(z), PD_(n), number average standard deviation (σ_(n)), and asymmetry(_(n)α₃). It is therefore advisable to feed the monomer in certainrelative rates at given H₂ activity (or partial pressure) in a givenreactor design or geometry. It should be clear that a very smallrelative feed rate (i.e. less than about 15 moles monomer/hr/molesactive Li) of the monomer to the catalyst will produce an undesiredlevel of reduced (essentially hydrogenated) monomer with some dimer.Furthermore the compositions produced have high asymmetry values and areless desired. On the other hand very high relative feed rates generallyform higher molecular weight distributions, such compositions that canotherwise be economically produced with little to no chain transfer.Because the molecular formula of the LOXSH catalyst is not of necessitydetermined, nor necessarily completely defined due to formation ofaggregates, nor is the molecular weight of the these catalystsaggregates known, the hourly feed rate of monomer (styrene) relative tocatalyst is suitably expressed in terms of the amount of active hydrideformed in the catalyst composition. It is assumed that each equivalentmole of active organolithium alkyl and/or active organomagnesium alkylforms one equivalent mole of a saline hydride; where the organolithiumcompounds provides one equivalent and the organomagnesium provides 2equivalents. Thus in the practice of this invention, the hourly feedrate of monomer to saline hydride compound should be in the range offrom about 10 to about 500 moles of monomer per hour per mole of activesaline hydride reagent charged in the reactor, or more preferably in therange of from about 65 to about 380 moles of monomer per hour per moleof saline hydride initially formed in the reactor. Again the equivalentmole of saline hydride is taken as being equal to the molar equivalentof the active organolithium alkyl and/or molar equivalents of the activeorganomagnesium alkyl initially charged. Again active organolithiumalkyl and/or molar equivalents of the active organomagnesium alkyl meansthe amount of organolithium alkyl and/or the amount of magnesium alkylradicals left after reaction with any and all protic species having apK_(a) less than H₂ present in the reaction mixture.

The temperature of the reaction mixture during the course of the monomerfeed is maintained in the range of about 20° C. to about 130° C., or inthe range of about 40° C. to about 99° C., or in the range of about 60°C. to about 90° C. It is conceivable that higher temperatures can beemployed during the entire run or during a portion of the run; howevertemperatures that accelerate any decomposition of the catalyst and/orcause the elimination of hydride from the polymer chains and formationof chain lengths terminated with unsaturated bonds are best avoided. Theamount of such hydride elimination termination reactions should varywith temperature and catalyst composition. In forming the LOXSHcatalysts and during the initial heat up, the catalyst can be combinedat the temperature just above the melting temperature of the hydrocarbonsolvent (or mixture of solvents) or the freezing point of the monomerthat is being fed. Combining the catalyst components at low temperatures(i.e. −10 to 15° C.) and even under cryogenic conditions (−10° C. to−126° C.) may have the benefit of avoiding or suppressing lithiation orother metalation reactions that can lead to partial decomposition of thepolytertiaryamine promotor and/or the polarizing complexing agents used.However conditions that result in precipitation of the saline hydridecatalyst or its precursor complexes and reagents are perhaps bestavoided.

The desired level of dispersal of monomer in the reaction medium willdepend upon the efficiency by which hydrogen is transported from thevapor phase and/or hydrogen gas feed to the condensed phase throughoutthe course of a run. Ideally a commercial scale, pilot scale and evenbench scale reactor can be designed and configured such that hydrogentransfer from the vapor phase to the condensed phase is essentiallyuniform throughout the course of the monomer feed. Under such uniformhydrogen transport between phases, it is desirable to minimize thereduction of monomer to its saturated analog by feeding the monomer suchthat a locally high concentration exists in the reactor. In bench orsmall pilot scale reactors such locally high monomer concentrations isaccomplished by employing very high relative monomer to catalyst feedrates and ratios with the use of relatively low feed velocities. Inlarge commercial equipment monomer is fed to a reaction zone which canbe physically apart or separated from the bulk of the reaction mixture(i.e. a pump-around-loop). The LOXLiH catalysts formed from2-[2-(dimethylamino)ethoxy]ethanol (DMAEOE) notwithstanding, theadvantage of the saline hydride catalyst of these HMSHIP processes ofthis invention is that such catalyst appears to be quite stable underthe process conditions and do not degrade catalyst activity or lead toimpurities derived from the polytertiaryamine promotor or theaminoalkoxide polarizing complexing agent used. Under these conditionsthe production of reduced monomer is kept to well under 10% of the totalmonomer charged. Dimer content can also be kept below 12% of the productdistribution and thus yields of trimer and above can well exceed 80% to90% based on monomer charged.

Upon completion of the LOXSH catalysts process monomer feed andreaction, as indicated, for example by rapid reduction in the processtemperature at constant heat flux and/or the termination of uptake ofH₂, the reaction mixture is maintained under hydrogen pressure and thentransferred to a wash reactor for quenching and water washing. The washreactor is charged with water (with or without a mineral acid such asH₂SO₄ and/or an organic acid such as acetic acid). Additionally the washreactor can be previously charged with an optional additional amount ofa solvent, preferably a hydrocarbon solvent. The quench can be conductedwith cooling or at ambient temperatures up to the temperature at whichthe hydrocarbon solvent forms an azeotrope with water under the pressureconditions of the wash reactor. The product is water washed to removealkali metal salts and at least a portion of the PTA promotor if presentand polarizing complexing agent. Under very acidic conditions suchreagents are nearly completely removed with the alkali and alkalineearth metal salts formed from the acid. Under basic conditions where anequivalent of acid or less is used the PTA promotor if present and thepolarizing complexing agent is partitioned between the organic reactionmixture and the aqueous wash. Water washing is continued until thedesired pH of the exiting wash water is obtained. Under basic conditionsa pH of 9 to a pH of 11 indicates that all the alkali and alkali earthmetal salts have been removed. Under acidic conditions, a pH of 6 to apH of 8 (depending on the alkalinity of the wash water) indicates thatall acidic species have been removed or at least neutralized.

When the wash is deemed complete solvent and a portion of any remainingpolytertiaryamine promoter as well as any remaining polarizingcomplexing agent (if it was present) and monomer reduction product arepreferably separated and recovered from the reaction mixture, wherebythe last traces of water are also removed azeotropically from thereaction mixture. This separation operation should be continued untilmonomer reduction product content of the resultant product mixture isless than about 0.1 wt %. Further modification and shaping of theproduct distribution by reducing the monomer dimer content is desirablefor some applications. For high boiling dimers this is easily conductedusing a wiped film evaporator.

The present invention relates a process of conducting hydrogen mediatedanionic polymerization of styrene (HMAPS) which under certain preferredconditions the formation of novel and beneficial low molecular weightanionic chain transfer polymer distributions low in asymmetry with verypure “head to tail” microstructure are formed in high yields. Theprocess features feeding styrene monomer to a suitable solvent thecontaining the [DMEA⁻]_(x)Li_(y)H_(z) catalyst under an atmospherecomprising molecular hydrogen wherein chain transfer from molecularhydrogen is the significant component of the mechanism that determinesthe number average molecular weight (M_(n)) of the resulting productdistribution including the ethylbenzene co-product. Thus the numberaverage molecular weight of the HMAPS product distribution is given bythe formula:

M_(n)=2+([styrene]/[H₂]*104)

Wherein [styrene] is the total amount of styrene fed and [H₂] is thetotal amount of hydrogen consumed over a period of time whether the timeis instantaneous or the entire period of the polymerization reaction.The product distribution formed from such a process when the monomer ishereinafter designated a HMAPS distribution. The shape in terms of theHMAPS M molecular weight distribution (i.e. M_(n), M_(w), M_(z); PD_(n),σ_(n) and asymmetry) is set and thereby controlled by the relative feedrate of styrene monomer to catalyst at a particular catalystconcentration and hydrogen partial pressure or activity.

The present invention also relates to a process for anionic chaintransfer polymerization comprising feeding a vinyl aromatic monomerand/or preferably a styrenic monomer to a reaction mixture under anatmosphere comprising molecular hydrogen in a reactor vessel having ahydrogen mediated chain transfer polymerization catalyst of the formulas[DMEA⁻]_(x)Li_(y)H_(z), wherein said catalyst is formed from the processof contacting: (i) about y equivalents of an organolithium compound;(ii) optionally TMEDA compound; (iii) about x equivalents ofdimethylamionethanol; (iv) optionally ethylbenzene; (v) a hydrocarbonsolvent with a pK_(a) greater than H₂; wherein the aromatic hydrocarbonand hydrocarbon solvent may be the same or different; and (vi) molecularhydrogen, wherein the amount of hydride formed z is given by theequation z=y−x and x, y and z are positive real numbers whole orfractional greater than zero; wherein said formula can further compriseN,N,N′,N′-tetramethylethylenediamine (TMEDA) ligand complex i.e.[DMEA⁻]_(x)Li_(y)H_(z).XTMEDA in a molar ratio X of moles TMEDA per moleof catalyst [DMEA⁻]_(x)Li_(y)H_(z) wherein X=0.0001 to about 8.0.

Thus the present invention further relates to an HMAPS process foranionic chain transfer polymerization comprising feeding styrene monomerto a reaction mixture under an atmosphere comprising H₂ in a reactorvessel, wherein said reaction mixture contains a catalyst having thechemical formulas [DMEA⁻]_(x)Li_(y)H_(z), wherein said catalyst isformed from the process of contacting: (i) about y equivalents of anorganolithium compound and/or an organomagnesium compound; (ii)optionally TMEDA compound; (iii) about x equivalents ofdimethylamionethanol; (iv) optionally ethylbenzene; (v) a hydrocarbonsolvent with a pK_(a) greater than H₂; wherein the aromatic hydrocarbonand hydrocarbon solvent may be the same or different; and (vi) molecularhydrogen; wherein the amount of hydride formed z is given by theequation z=y−x and x, y and z are positive real numbers whole orfractional greater than zero and wherein the solubility of hydridecomprising said catalyst or reagent is at least about 0.0080 moles perliter.

The same non-limiting examples and amounts of the components listedabove for forming the [DMEA⁻]_(x)Li_(y)H_(z) catalyst as well as used inthe above catalytic and or reagent compositions may be used forconducting the [DMEA⁻]_(x)Li_(y)H_(z) HMAPS processes and need not berepeated.

The hydrocarbon solvent which may be used is any hydrocarbon having apK_(a) greater than molecular hydrogen (H₂) under the reactionconditions. Non-limiting examples of preferred such solvents arecyclohexane, methylcyclohexane, used with or without ethylbenzene. Otherhydrocarbon solvents can be used as long as their use does notaffect: 1) the solubility of the saline hydride catalyst, reactiveintermediates, transient living polymer chains and the polymer chaindistribution product; or 2) act as an organic chain transfer agent ofsufficient activity that the hydrocarbon solvent is incorporated in theHMAPS product distribution at a level of 2 wt % or more.

In conducting the HMAPS process of this invention in order to form themost desired HMAPS distributions of this invention the monomer feedrelative to lithium hydride is generally in the range of from about(10:1) to about (1000:1), preferably from about (50:1) to about (800:1)and most preferably (100:1) to about (600:1) with a lithium hydrideconcentration of about 200 ppm to about 750 ppm at the start of a runand from about 65 ppm to about 350 ppm at the end of the run for asemi-batch operation of this process depending the total amount ofstyrene monomer is fed. For a continuous mode of operation, it ispreferred to operate the process such that the lithium hydrideconcentration is between from about 200 ppm to about 500 ppm throughoutthe course of the operation.

In the batch or semi-batch operation of the process technology of thisinvention the monomer (i.e. styrene) is fed with time to the reactionmedium, hence the initial ratio monomer to [DMEA⁻]_(x)Li_(y)H_(z)catalyst formed at the very instant that the vapor from the first dropor increment of monomer fed mathematically approaches the limit (1: ∞).Thus a total monomer charged to the initially formed saline lithiumhydride molar ratio outside the preferred recited ranges—i.e. a molarratio in the range of from the limit of (1.00:∞ to 1.00:0.101) which isabout (1:10,000 to about 9.9:1.0) monomer to [DMEA⁻]_(x)Li_(y)H_(z)catalyst formed—are demonstrated as workable ranges at the outset ofeach of the Examples provided below. However the monomer feed isgenerally continued until the higher desired monomer to lithium hydrideratio is complete. The practice of a charge molar ratio limited to(1:10,000 to about 9.9:1.0) is within the scope of the invention butsimply represent uneconomical utilization of the organolithium compoundused in forming the [DMEA⁻]_(x)Li_(y)H_(z) catalyst.

Conversely feeding monomer at a relative molar ratio to[DMEA⁻]_(x)Li_(y)H_(z) catalyst initially greater than about 1000:1 canbecome unworkable due to viscosity levels; resulting in diminished chaintransfer thereby producing compositions of undesired molecular weightdistributions (MWD). The [DMEA⁻]_(x)Li_(y)H_(z) catalyzed processtechnology features ease in forming the catalyst, selectivity withregard to microstructure and finally high catalyst activity. In Examples14 and 15 it is demonstrated that an catalyst efficiency of 15,000% canbe achieved using a >600:1 monomer:lithium hydride charge ratio. Thecombination of these two runs produced a dimer stripped polymerdistribution characterized as having M_(w)=730 with PD_(n)=1.4 in 75%isolated yield.

The monomer feed rates relative to the amount of [DMEA⁻]_(x)Li_(y)H_(z)catalyst is among the determining kinetic factors with regard to settingthe polymer composition's polydispersity, PD_(n), and hence the overallmolecular weight distribution (MWD) as measured by the values of M_(n),M_(w), M_(z), PD_(n), number average standard deviation (σ_(n)), andasymmetry (_(n)α₃). It is therefore advisable to feed the monomer incertain relative rates at given H₂ activity (or partial pressure) in agiven reactor design or geometry. It should be clear that a very smallrelative feed rate (i.e. less than about 15 moles monomer/hr/molesactive Li) of the monomer to the catalyst will produce an undesiredlevel of reduced (essentially hydrogenated) monomer with some dimer.Furthermore the compositions produced have high asymmetry values and areless desired. On the other hand higher relative feed rates generallyform higher molecular weight distributions with lower yield ofethylbenzene and styrene dimer. HMAPS Compositions having M_(w) in therange of 850 to 1050 can be easily prepared in from about 82% to about90% yield after stripping ethylbenzene (yields as low as 4% to 6% yield)and dimer (yields as low as 8% to 12% yield).

The temperature of the reaction mixture during the course of the monomerfeed is maintained in the range of about 20° C. to about 130° C., or inthe range of about 40° C. to about 99° C., or in the range of about 60°C. to about 90° C. It is conceivable that higher temperatures can beemployed during the entire run or during a portion of the run; howevertemperatures that accelerate any decomposition of the catalyst and/orcause the elimination of hydride from the polymer chains and formationof significant levels of chain length distributions terminated withunsaturated bonds are best avoided. The amount of such hydrideelimination termination reactions may vary with temperature and catalystcomposition.

The desired level of dispersal of monomer in the reaction medium willdepend upon the efficiency by which hydrogen is transported from thevapor phase and/or hydrogen gas feed to the condensed phase throughoutthe course of a run. Ideally a commercial scale, pilot scale and evenbench scale reactor can be designed and configured such that hydrogentransfer from the vapor phase to the condensed phase is essentiallyuniform throughout the course of the monomer feed. Under such uniformhydrogen transport between phases, it is desirable to minimize thereduction of monomer to its saturated analog by feeding the monomer suchthat a locally high concentration exists in the reactor. In bench orsmall pilot scale reactors such locally high monomer concentrations isaccomplished by employing very high relative monomer to catalyst feedrates and ratios with the use of relatively low feed velocitiescontrolled by feed rate (volume/sec) and the area (set by the radius fora cylindrical feed tip) through which the monomer is fed (i.e. cc/secdivided by square cm). In large commercial equipment monomer can be fedto a reaction zone which can be physically apart or separated from thebulk of the reaction mixture (i.e. a pump-around-loop). The[DMEA⁻]_(x)Li_(y)H_(z) catalysts have the advantage in that suchcatalyst appears to be quite stable under the process conditions and donot suffer from degradation of catalyst activity and thus do not lead tothe formation of impurities derived from the polytertiaryamine promotoror the aminoalkoxide polarizing complexing agent used. Under the HMAPSprocess conditions the formation of reduced ethylbenzene is kept to wellbelow 10% of the total monomer charged. Dimer content can also be keptbelow 12% of the product distribution. Yields of HMAPS distributionsstripped to less than 2% preferably less than 1% styrene dimer contentand thus comprising >98% trimer and above can well exceed 80% to 90%based on total monomer charged.

Once the components are combined in the desired charge ratios thecatalyst and further activated if desired, the catalyst is then readyfor use for the hydrogen mediated anionic polymerization process of thisinvention. Thus styrene monomer is fed to the [DMEA⁻]_(x)Li_(y)H_(z)catalyst composition under a partial pressure of hydrogen between about0.001 to about 10.0 Bar, or about 0.3 to about 6.8 Bar, or about 0.5 toabout 5.2 Bar or about 1.0 to about 4.2 Bar. A hydrogen partial pressuregreater than about 10.0 Bar is permissible for a period of time duringthe process when process conditions entail routine operation withadequate mixing to maintain hydrogen transfer to the condensed phase.However a substantial amount of time at such increased hydrogen partialpressures will generally result in hydrogenation of the monomer with asubstantial reduction of polymer molecular weight with an increase yieldof ethylbenzene. Conversely, hydrogen pressures below about 0.1 Bar(less than 1.5 PSI) are permissible during routine operation of theprocess but will result in a composition of high asymmetry with a veryhigh molecular weight tail having a 10% high molecular weight aboveabout 2000 Daltons as measured by GPC. Formation of such compositionswith high asymmetry also occurs when reaction conditions result in poorhydrogen mass transfer to the condensed phase. Formation of such highmolecular weight tails as a feature of the product molecular weightdistribution is observed when feeding monomer for short periods of timeunder inadequate mixing conditions which create a reaction medium ofincreased viscosity. The increased viscosity makes mass transfer ofhydrogen increasingly inefficient resulting even more increasedviscosity. Reaction conditions that can result in increased viscosityare: 1) reaction temperature; and/or 2) less than optimum catalystconcentration; and/or 3) less then optimum monomer to catalyst chargeratio; and/or 4) too high of a localized monomer concentration: and/or5) periods of the feed when mixing has become inefficient due to poorreactor geometry/design. Thus it is therefore pointed out that thepartial pressures recited above are only meaningful if adequate masstransfer of molecular hydrogen to the condensed phase is maintained suchthat the partial pressure reflects the condensed phase activity ofmolecular hydrogen—i.e. a steady state mass transfer of H₂ to thecondensed phase is established. Thus much higher H₂ partial pressurescan be applied when mass transfer to the condensed phase is diminisheddue to poor mixing of the vapor phase with the condensed phase and thusresults in poor mass transfer. However if viscosity becomes too great,then increased mixing generally results in formation of a foam and evenless efficient mass transfer to the condensed phase.

Upon completion of the [DMEA⁻]_(x)Li_(y)H_(z) catalyst HMAPS processstyrene monomer feed and reaction, as indicated, for example by rapidreduction in the process temperature at constant heat flux and/or thetermination of uptake of H₂, the reaction mixture is maintained underhydrogen pressure and then transferred to a wash reactor for quenchingand water washing. The wash reactor is charged with water (with orwithout a mineral acid such as _(H2)SO4 and/or an organic acid such asacetic acid). Additionally the wash reactor can be previously chargedwith an optional additional amount of a solvent, preferably ahydrocarbon solvent. The quench can be conducted with cooling or atambient temperatures up to the temperature at which the hydrocarbonsolvent forms an azeotrope with water under the pressure conditions ofthe wash reactor. The product is water washed to remove alkali lithiumsalts and at least a portion of the TMEDA promotor if present andpolarizing complexing agent. Under very acidic conditions such reagentsare nearly completely removed with the alkali and alkaline earth lithiumsalts formed from the acid. Under basic conditions where an equivalentof acid or less is used the TMEDA promotor if present and the DMEAHreagent is partitioned between the organic reaction mixture and theaqueous wash. Water washing is continued until the desired pH of theexiting wash water is obtained. Under basic conditions a pH of 9 to a pHof 11 indicates that all the alkali and alkali earth lithium salts havebeen removed. Under acidic conditions a pH of 6 to a pH of 8 (dependingon the alkalinity of the wash water) indicates that all acidic specieshave been removed or at least neutralized. It may be desirable at timesunder acidic wash conditions to add a small (20 mg for two liter run)amount of a surfactant such as sodium dodecylsulfate to disrupt anyemulsion or micelle formation

When the wash is deemed complete solvent and a portion of any remainingpolytertiaryamine promotor as well as any remaining polarizingcomplexing agent (if it was present) and ethybenzene co-product arepreferably separated and recovered from the reaction mixture, wherebythe last traces of water are also removed azeotropically from thereaction mixture. This separation operation should be continued untilethylbenzene co-product content of the resultant product mixture is lessthan about 0.1 wt %. Modification with essentially complete removal ofethylbenzene is achieved by further shaping the HMAPS distribution byreducing the styrene dimer content by distillation preferably with awiped film evaporator.

In comparison to other prior art technologies (e.g. EPO 741147), theHMAPS process featuring the ability to form the lithium alkoxides insitu is both a laboratory convenience and a major commercial advantagein forming a hydrocarbon soluble saline metal hydride catalyst. Thuswhen forming the LOXLiH and LOXMgH₂ catalyst, forming the lithium and/ormagnesium alkoxide reagent precursor in situ: (1) avoids the handling offlammable air and moisture reactive solids; (2) eliminates dissolving ametal alkoxide in a concentrate of the large molar excesses of thepolytertiaryamine promotor; (3) eliminates the need to remove tracelevels of by product alcohol from process streams prior to recycle ofsolvents and other reagents, and (4) greatly reduces and in someembodiments eliminates the amount of polytertiaryamine promotor needed.Both the LOXLiH and LOXMgH₂ catalyst appears to be more uniformlysoluble in the catalyst forming and/or polymerization reaction mixture.Thus run to run variability is deemed to be substantially improved—morereproducible—hence resulting in an even more robust commercial processthan the SASH processes of Examples 38 and 39 or the HASH process ofExample 40. The LOXLiH and LOXMgH₂ catalysts also appear to leave littleif any substantial amount of undesired solids on the walls and internalparts of the polymerization reactor and other associated equipment.Insoluble catalyst deposits on reactor surfaces are a significantcomplication associated with prior art organic chain transfer processeswhere the catalyst is formed from reagents such as n-butyllithium,potassium t-butoxide, TMEDA and ethylbenzene under inert atmospheressuch as nitrogen.

The fortuitous advantage of the LOXLiH and LOXMgH₂ catalyst as well asthe hydrogen mediated anionic chain transfer processes which theycatalyze, is that these catalyst and processes provide pure chaintransfer polystyrene compositions with microstructures free offragmentation polymerization and chain isomerization impurities orimpurity distributions. This has been experimentally demonstrated byanalyzing the first 4 to 6 oligomers by gas chromatography (see FIGS. 3and 4 which compare LOXLiH PS oligomer microstructure with that of priorart ethylbenzene chain transfer polymerization PS derived oligomers).The LOXKH catalyst process as well as the HASH and SASH processesgenerally produce polystyrene compositions with less desiredmicrostructures (see FIGS. 5-7), which are also common to the priortechnologies (see also FIGS. 12-14). Thus, the LOXLiH PS and LOXMgH₂ PScompositions are greatly advantageous in forming commercial productderived from further chemistry such as aromatic electrophilicsubstitution reactions conducted upon the product distributions. Itshould be understood that judicious selection of the aminoalcoholcomponent—including optically active aminoalcohols—of the catalyst,along with further experimentation, the practitioner of this inventionmay discover methods of controlling other microstructure features suchas tacticity for vinyl aromatic polymers.

Thus another embodiment of this invention are anionic chain transferstyrenic polymer distributions initiated with a saline hydride andhaving a polymer microstructure that is greater than 97% head to tailmicrostructure, more preferably greater than 98% head to tailmicrostructure and most preferred greater than 99% head to tailmicrostructure as depicted by the polymeric polystyrene structure 12above (shown specifically for but not limited to styrene). Stated inanother way, the anionic chain transfer styrenic polymer compositions ofthis invention are initiated via addition of a saline hydride to astyrenic monomer and have chain length distributions wherein less than3.0%, more preferably less than 2.0% and most preferably less than 0.8%of the polymer chains have one or more quaternary carbons in the polymermicrostructure. Additionally said distributions of the hydride initiatedpoly(styrenic) structure (again shown specifically for but not limitedto styrene) 12 above comprise less than 3%, more preferably less than 2%and even more preferably less than 1% and most preferably less than 0.2%to an amount below the detection limit of the chain lengthdistribution(s) as a coproduct distribution(s) arising from afragmentation polymerization processes where the microstructure andpurity of the chain length distribution is determined vide infra fromgas chromatographic analyses of the lowest molecular weight chainsobtained from said hydrogen mediated saline hydride initiatedpolystyrene or poly(styrenic) or poly(vinylaromatic) distributions wheren=0 to n=4 of the above polymer structure:

The most preferred initially formed hydrogen mediated saline hydrideinitiated styrenic distributions are formed exclusively from styrenemonomer and hydrogen and have a chain length distribution of the abovestructure (12). Said chain length distribution is comprised of i−1discrete polymer chain lengths in a statistical number averagedistribution of the relative molar content where i is the total numberof monomers incorporated in a given discrete polymer chain. The number iis a positive integer from i=2 to i=i. Thus for (Chain-1) when n=0(styrene dimer) then i=2; (Chain-2) when n=1 (styrene trimer) then i=3;(Chain-3) n=2 (styrene tetramer) then i=4; (Chain-4) when n=3 (styrenepentamer) then i=5; (Chain-5) when n=4 (styrene hexamer) then i=6; . . .and (Chain-(i−1)) when n=i−2 then i=i. Thus the (i−1)^(th) discretepolymer chain is the discrete polymer chain of the greatest chainlength. We have found that in general the GPC MWD analysis results forthe polymer compositions of this invention can be reasonably modeledwith a Gamma probability density function (PDF). More importantlyhowever we have found that compositions formed from a catalyst otherthan the monometallic lithium based LOXLiH catalyst are generally moreaccurately modeled with a Beta PDF. Most importantly the LOXLiH PS GPCMWD results are accurately modeled by the Weibull PDF—which wouldindicate that for the LOXLiH catalyzed system the molecular weightdistribution is set by chain transfer alone without significantregeneration of dead polymer chains as well as may indicate noactivation, participation or incorporation of ethylbenzene as an organicchain transfer agent in forming the polymer distribution.

The molecular weight distributions of the chain length distributions ofthis invention when styrene is the monomer are characterized where M_(n)is in the range of from 315 to 934 Daltons; M_(w) is in the range offrom about 392 to about 1705 Daltons; and M_(z) is in the range of about512 to 2930 Daltons; PD_(n) is in the range of 1.24 to 1.82; with astandard deviation in the range of 156 to 849 Daltons and the asymmetryis in the range of 1.40 to about 3.00. More preferred compositions havemolecular weight distributions where M_(n) is in the range of from 410to 680 Daltons; M_(w) is in the range of from about 553 to about 1205Daltons; and M_(z) is in the range of about 745 to 1950 Daltons; PD_(n)is in the range of 1.29 to 1.82; with a standard deviation in the rangeof 257 to 600 Daltons and the asymmetry is in the range of 1.50 to about2.60. Most preferred compositions have molecular weight distributionswhere M_(n) is in the range of from 444 to 683 Daltons; M_(w) is in therange of from about 600 to about 1150 Daltons; and M_(z) is in the rangeof about 798 to 1768 Daltons; PD_(n) is in the range of 1.35 to 1.68;with a standard deviation in the range of 263 to 565 Daltons and theasymmetry is in the range of 1.50 to about 2.31.

Preferred non-blended compositions of this invention are comprisedessentially only if not solely of styrene, have greater than 97 wt %“Head to Tail” microstructure and have had their chain lengthdistribution further shaped or modified by removal of a portion of thelowest molecular weight chains. Removal of the lower molecular weightchains, especially styrene dimer—like removing the lowest value(s) or aportion of the lowest value(s) from all other arithmetic averages (e.g.a grade point average)—results in a new average with an increasedoverall molecular weight distribution. Thus the preferred modifiedmolecular weight distributions of this invention will overlap with theunaltered distributions but may not lie within the range of molecularweight distributions or molecular weight parameters specified abovebecause of the simple numerical consequence of having been altered bythe removal of a portion of the lower molecular weight fraction of thedistribution. Thus preferred compositions where the dimer content hasbeen reduced but is still present and represents about 0.1 to about 1.0wt % (as determined by GPC analysis) of the entire distribution havemolecular weight or chain length distributions where M_(n) is in therange of from 407 to 1018 Daltons; M_(w) is in the range of from about487 to about 1741 Daltons; and M_(z) is in the range of about 579 to2938 Daltons; PD_(n) is in the range of 1.40 to 1.71; with a standarddeviation in the range of 180 to 858 Daltons and the asymmetry is in therange of 1.31 to about 3.016. More preferred compositions have molecularweight distributions where M_(n) is in the range of from 494 to 788Daltons; M_(w) is in the range of from about 623 to about 1278 Daltons;and M_(z) is in the range of about 782 to 1964 Daltons; PD_(n) is in therange of 1.26 to 1.62; with a standard deviation in the range of 253 to621 Daltons and the asymmetry is in the range of 1.40 to about 2.40.Most preferred compositions have molecular weight distributions whereM_(n) is in the range of from 521 to 737 Daltons; M_(w) is in the rangeof from about 661 to about 1202 Daltons; and M_(z) is in the range ofabout 827 to 1783 Daltons; PD_(n) is in the range of 1.27 to 1.63; witha standard deviation in the range of 270 to 586 Daltons and theasymmetry is in the range of 1.40 to about 2.50.

It is pointed out that blending operations where statisticaldistributions are combined can result in non-statistical distributionswhere the constraints provided for PD_(n), standard deviations would notbe applicable. However such blends are within the scope of thisinvention in that they are formed by combination of compositions of andformed from this invention.

Thus another embodiment of this invention are LOXLIH PS distributionsdesignated as HMAPS distributions. Such HMAPS distributions have M_(n)[styrene]/[H₂] and M_(w) and M_(z) set or by the relative feed rate ofstyrene to catalyst at for a given catalyst composition, catalystconcentration and hydrogen pressure. HMAPS distributions are initiatedwith a lithium hydride, terminated by a proton from hydrogen and possessa polymer microstructure that is greater than 97% head to tailmicrostructure, more preferably greater than 98% head to tailmicrostructure and most preferred greater than 99% head to tailmicrostructure as depicted by the polymeric polystyrene structure 12above. Stated in another way, the HMAPS polymer compositions of thisinvention are initiated via addition of lithium hydride to a styrenemonomer and have chain length distributions wherein less than 3.0%, morepreferably less than 2.0% and most preferably less than 0.8% of thepolymer chains have one or more quaternary carbons in the polymermicrostructure. Additionally the HMAPS distributions of 12 abovecomprise less than 3%, more preferably less than 2% and even morepreferably less than 1% and most preferably less than 0.2% to an amountbelow the detection limit of the chain length distribution(s) as acoproduct distribution(s) arising from a fragmentation polymerizationprocesses where the microstructure and purity of the chain lengthdistribution is determined vide infra from gas chromatographic analysesof the lowest molecular weight chains obtained from the HMAPSdistributions where n=0 to n=2 of the polymer structure 12 above.

The most preferred initially formed HMAPS distribution have chain lengthdistribution is comprised of i−1 discrete polymer chain lengths in astatistical number average distribution of the relative molar contentwhere i is the total number of monomers incorporated in a given discretepolymer chain. The number i is a positive integer from i=2 to i=i. Thusfor (Chain-1) when n=0 (styrene dimer) then i=2; (Chain-2) when n=1(styrene trimer) then i=3; (Chain-3) n=2 (styrene tetramer) then i=4;(Chain-4) when n=3 (styrene pentamer) then i=5; (Chain-5) when n=4(styrene hexamer) then i=6; . . . and (Chain-(i−1)) when n=i−2 then i=i.Thus the (i−1)^(th) discrete polymer chain is the discrete polymer chainof the greatest chain length. We have found that in general the GPC MWDanalysis results for the polymer compositions of this invention can bereasonably modeled with a Gamma probability density function (PDF). Moreimportantly however we have found that HMAPS distributions are ingeneral model quite well by the Weibull PDF. This in then interpreted tomean the polymerization process is limited to the steps of: i)initiation; ii) chain propagation; and iii) chain termination almostexclusively if not exclusively by hydrogen mediation, i.e. ethylbenzeneis not kinetically active as a chain transfer agent.

The molecular weight distributions of the HMAPS compositions of thisinvention are characterized by GPC (UV detector) analysis wherein theM_(n) is in the range of from 400 to 800 Daltons; the M_(w) is in therange of from about 600 to about 1200 Daltons; the PD_(n) is in therange of about 1.35 to about 1.75; the standard deviation is in therange of about 270 to about 550 Daltons and the M_(w) 10% High is lessthan about 3300 Daltons. More preferred compositions are HMAPS polymer,distributions are characterized as measured by GPC (UV detector)analysis wherein the M_(n) is in the range of from about 400 to about800 Daltons; the M_(w) is in the range of from about 600 to about 1200Daltons; the M_(z) is in the range of about 750 to about 1500 Daltons;the PD_(n) is in the range of about 1.35 to about 1.75; the standarddeviation is in the range of about 270 to about 550 Daltons; theasymmetry is in the range of about 1.60 to about 2.2; and the M_(w) 10%High is less than about 2400 Daltons.

Preferred HMAPS distributions of this invention are comprisedessentially only if not solely of styrene, have greater than 97 wt %“Head to Tail” microstructure and have had their chain lengthdistribution further shaped or modified by removal of a portion of thelowest molecular weight chains. Removal of the lower molecular weightchains, especially styrene dimer results in a new higher value for eachmoment of the molecular weight distribution (i.e. M_(n); M_(w); andM_(z)) and thus an increased and alteration of the overall MWD. Thus thepreferred modified molecular weight distributions of this invention willoverlap with the unaltered distributions but may not lie within therange of molecular weight distributions or molecular weight parametersspecified above because of the simple numerical consequence of havingbeen altered by the removal of a portion of the lower molecular weightfraction of the distribution. Thus preferred HMAPS distributions whereinthe dimer content has been reduced but is still present and representsfrom about 0.1 to about 1.5 wt % (as determined by GPC analysis UVdetector) of the entire distribution have molecular weight or chainlength distributions where M_(n) is in the range of from about 500 toabout 800 Daltons; M_(w) is in the range of from about 650 to about 1200Daltons; and M_(z) is in the range of about 900 to about 1500 Daltons;PD_(n) is in the range of about 1.25 to about 1.70; with a standarddeviation in the range of about 280 to about 600 Daltons; the asymmetryis in the range of about 1.45 to about 3.20; and a M_(w) 10% High in therange of about about 1500 Daltons to about 3500 Daltons.

It is pointed out that blending operations where statisticaldistributions are combined can result in non-statistical distributionswhere the constraints provided for PD_(n), standard deviations would notbe applicable. However such blends are within the scope of thisinvention in that they are formed by combination of compositions of andformed from this invention.

Thus this invention also relates polymeric flame retardant compositionsformed from electrophilic aromatic bromination of pure polystyrenecompositions. Said brominated polystyrene compositions having beenprepared by processes that entails bromination with bromine and abromination catalyst in a solvent, or other known bromination processesfor polystyrene compositions, formed from the saline hydride initiatedhydrogen mediated anionic polymerization of styrene monomer. Thus thisinvention provides flame retardant composition comprising a brominatedpolystyrene of the HMAPS distributions described above, wherein thecomposition: (i) has a bromine content in the range of about 73 wt % toabout 77 wt %; (ii), a thermal HBr value at 300° C. below the detectionlimit of 50 ppm and no more than about 1000 ppm, the wt % and ppm valuesbeing based upon the total weight of the composition; athermogravimetric (TGA) weight loss of 5% occurring at a temperaturegreater than about 355° C. to about 375° C.; and a glass transitiontemperature in the range of about 110° C. to about 155° C.

Components referred to by chemical name or formula anywhere in thespecification or claims hereof, whether referred to in the singular orplural, are identified as they exist prior to coming into contact withanother substance referred to by chemical name or chemical type (e.g.,another component, a solvent, or etc.). It matters not what chemicalchanges, transformations and/or reactions, if any, take place in theresulting mixture or solution as such changes, transformations, and/orreactions are the natural result of bringing the specified componentstogether under the conditions called for pursuant to this disclosure.Thus the components are identified as ingredients to be brought togetherin connection with performing a desired operation or in forming adesired composition. Also, even though the claims hereinafter may referto substances, components and/or ingredients in the present tense(“comprises”, “is”, etc.), the reference is to the substance, componentor ingredient as it existed at the time just before it was firstcontacted, blended or mixed with one or more other substances,components and/or ingredients in accordance with the present disclosure.The fact that a substance, component or ingredient may have lost itsoriginal identity through a chemical reaction or transformation duringthe course of contacting, blending or mixing operations, if conducted inaccordance with this disclosure and with ordinary skill of a chemist, isthus of no practical concern.

The invention described and claimed herein is not to be limited in scopeby the specific examples and embodiments herein disclosed, since theseexamples and embodiments are intended as illustrations of severalaspects of the invention. Any equivalent embodiments are intended to bewithin the scope of this invention. Indeed, various modifications of theinvention in addition to those shown and described herein will becomeapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

The following Examples illustrate the present invention. It is to beunderstood, however, that the invention, as fully described herein andas recited in the Claims, is not intended to be limited by the detailsof the following Examples.

EXAMPLES General Apparatus Used

The apparatus used for HMSHIP processes is as follows. A 316 stainlesssteel 2-liter Parr autoclave having thermal couple, bottom drain valve,cooling coils, hot oil jacket and either two or three or fourpitch-blade turbine impellers (with placement of each impeller as notedbelow and specified in the Examples) was further equipped with a pistonpump, a diaphragm pump, nitrogen purged 250 ml stainless charge vessel,a well calibrated high pressure metering pump and a 1/16th inch ODsubsurface monomer feed line having either a 0.02″, or a 0.01″ or a0.007″ ID terminal section (as noted or as otherwise noted in theExamples). The magnetic drive on the agitator is connected to a highspeed air driven motor and generally operated (unless otherwise noted inthe Examples) such that the stirrer impellers spin at a rate of 1130±25RPMs during the polymerization. The autoclave is vented to an oilbubbler and/or to a 6-liter oil jacketed creased wash vessel having abottom drain and outfitted for overhead stirring and distillation. Thebottom drain valve and the dip-leg sampling port of the autoclave areboth plumbed to the wash vessel for direct transfer of the unquenchedreaction mixture. Bulk solvent (e.g., cyclohexane or methylcyclohexaneor ethylbenzene or mixtures thereof recovered from a previous run) ischarged to the reactor via piston pump through the charge vessel. Thecatalyst components (e.g., TMEDA/potassium t-butoxide/solvent solutionand butyllithium) are charged separately to the reactor through thecharging vessels with the flow rate controlled with a fine meteringVernier handle needle valve. The contents of the charge vessel arepressure transferred with a minimum of nitrogen bsck-pressure to theautoclave having either nitrogen or a hydrogen or a hydrogen/nitrogenatmosphere. Styrene is fed via high pressure metering pump through basicalumina columns (1 or 20.5″ O.D columns each w/ 11.0 g of 60-325 meshAl₂O₃) to remove the inhibitor at predetermined constant rate. Hydrogenis fed to the head space and/or subsurface and maintained at the desiredpressure. The autoclave reactor is heated with oil having a temperatureset point at or just above (+1° C. to +3° C.) the desired reactiontemperature and the reaction temperature was tightly maintained at thepredetermined set point once the reactor controller lined out (generallyafter the first 20-30 minutes of the monomer feed when starting atambient temperature). Thus the reaction temperature might have briefexcursion in temperature generally no more than 5° C. above the desiredset-point temperature.

During the course of the development of this invention 4 separateconfigurations (Configurations I-IV below) or placements involving two,three or four pitch-blade turbine impellers was utilized:

-   -   I. Two pitch blades with the first 6.25″ and the second 10.0″        from the top of the reactor    -   II. Three pitch blades with the first 6.0″, the second 8.0″, and        the third 10″ from the top of the reactor.    -   III. Three pitch blades with the first 5.0″, the second 7.0″,        and the third 10″ from the top of the reactor.    -   IV. Four pitch blades with the first 4.0″, the second 6.0″, the        third 8″ and the fourth 10″ from the top of the reactor.

The 2-liter autoclave is a cylinder having 10 inches in depth, thus eachinch represents 200 ml of volume. Configuration II and III with threeimpellers resulted in uniform uptake of hydrogen throughout the courseof the feed so long as the feed was limited such that the total volumein the reactor did not significantly go above the level where the topimpeller became ineffective at mass transfer. Configuration IV with theuse of 4 pitched blade impellers is the preferred configuration foroperation of this invention—especially with the LOXSH catalyst of thisinvention—in the Parr 2-liter reactor, this configuration allowed forthe full use of the reactor's volume with uniform mass transfer of thevapor space to the condensed phase and hence uptake of hydrogenthroughout the styrene monomer feed. In that the polymerization reactoris 2000 ml in volume having a maximum working volume of 1750 ml and theinitially formed reaction mixture is typically 400 to 600 ml in volume,then the maximum volume of styrene that can be safely fed is in therange of 1350 ml to 1150 ml (not accounting for temperature or changesin density upon polymerization). Thus feeding such volumes of styrene(1150 ml to 1350 ml) is deemed as a full charge of styrene or of monomerfor this reactor configuration. The terms full charge of styrene orpartial charge of styrene or any term or other phrase used to imply afractional portions of styrene charged are limitations or restrictionsfor the apparatus as described above and in no way represents alimitation on the processes or practice of this invention in a reactorsystem(s) having a different reactor geometry or configuration or modeof operation (batch, semi-batch, semi-continuous, continuous, back-mixedor plugged flow are all modes and/or configurations within the scope ofthis invention). The Examples recited below are representative of batchor semi-batch operations of this invention. Clearly one of ordinaryskill in the art can take the teachings of these Examples and extend theapplication of this invention to include modes of operation that entailcontinuous operation with and/or without some level of back mixing andaccordingly such modes are well within the scope of this invention.

When charges are made to the polymerization reactor under a nitrogenatmosphere, the autoclave reactor is purged at least 3 times bypressurizing and then venting with 65 PSIG H₂ (65 PSIG vented to 0PSIG). The polymerization reactor is then pressurized to the desired H₂pressure. If reactor charges are made to the reactor containing ahydrogen atmosphere, then the reactor is typically pressurized andvented 2 times with 50 PSIG H₂. Styrene (99%, Acros), TMEDA (Aldrich),2-methoxymethanol (99.9% Aldrich HPLC grade), 2-N,N-dimethylethanolamine(99.5% Aldrich), 2-[2-(dimethylamino)ethoxy]ethanol (98%, Aldrich),Potassium Hydride (30% in mineral oil, Aldrich), di-n-butylmagnesium 1.0M in heptanes and n-butyllithium (2M in Cyclohexane (Aldrich) are eachused as received from the vendor. Anhydrous cyclohexanemethylcyclohexane and ethylbenzene (all Aldrich) are handled under aninert dry nitrogen atmosphere.

Examples 1-24

The experimental details of Examples 1-24 (reaction conditions, reagentcharges, and initial as well as final catalyst concentration), scale-upparameters (relative feeds and relative hourly feed rates) and results(polymer molecular weight distribution [MWD] as determined by GPC andpolymer yield) are presented in tabular form in Tables III-VI. It shouldbe clear that the LOXSH catalyst and polymerization reaction conditionsof this invention provide countless combinations of the reagents fromwhich they are synthesized and the reaction parameters under which aprocess is conducted. Thus Examples 1-5 and Examples 6-13 comprise theinitial scoping experiments designed to explore this novel catalystsystem and reaction conditions. Accordingly these Examples only utilizedabout 25% to 50% of the preferred amount of monomer per experiment. Withthe reduced amount of styrene monomer employed, impeller configurationII was employed. Therefore except for the placement of the impellers inthe polymerization reaction and the shortened styrene monomer feed, thepreparation and execution of these experiments was essentially the sameas Examples 14-24. Thus Examples 3, 14-15, 20-21 and 24 are deemedrepresentative and are described in greater detail. It should be notedthat GC analyses of the four to six most volatile styrene oligomers ofthe LOXLiH PS compositions thus produced (Examples 1-24) demonstrated99.4% to 99.9% of the discrete polymer chains have pure linear “head totail” polymer microstructure. Additionally these LOXLiH PS compositionsare essentially free of any fragmentation polymerization impurities orco-product distributions. On an individual monomer repeating unit basis,statistical models (Weibull PDF) of these distribution indicate thatbetween 99.986 mole % and 99.999 mole % of the styrene repeating unitshave either 2° (methylene) or 3° (methine) benzylic carbon atoms. Put inanother way, these LOXLiH PS compositions have less than 10 ppm to nomore than 140 ppm quaternary carbon “tail to head to tail” linkages inthe microstructure.

Example 3 Representative of 25% of Full Monomer Feed Volume LOXLiH Ca.[DMEA⁻]₅Li₁₂H₇ Catalyst at 80° C.

Anhydrous cyclohexane, 345 ml of 495 ml (384.9 g) was charged to thereactor at 25° C. under a dry hydrogen (0 PSIG H₂) atmosphere. To thestirred solvent (800 RPM, three pitched blade turbines withConfiguration II above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 2.27 g(0.0255 mol.) N,N-dimethylethanolamine, 134.7 g (1.27 mol) ethylbenzeneand 12.22 g (0.105 mol) of TMEDA. The charge vessel and transfer line tothe reactor was flushed with a 50 ml portion of anhydrous cyclohexanefrom the total amount above. Next, 30.37 ml (0.0607 mole) 2.0 Mn-butyllithium was transferred through the charge vessel to the reactorfollowed by two 50 ml aliquots of the anhydrous cyclohexane from thetotal amount above. During the organolithium charge agitation speed wasincreased to 1130 RPM and consequently the reactor pressure decreased to−3 PSIG over the course of the 15 minute charge period as hydrogen wasconsumed. The reactor head space was purged and vented with 21 PSIG dryH₂ (through a subsurface feedline) two times (slowly venting to keep thecontents from foaming out of the reactor) leaving the reactor at 0 PSIG.The reactor was then heated to 70° C. with the pressuring building to 4PSIG. The heating was conducted with 81° C. oil on the reactor jacket.Upon reaching 70° C. the styrene monomer feed was initiated, feeding257.2 g g (2.47 mol.) of styrene. The styrene was fed through asubsurface feed line (0.02″ ID tip, 2.02 ft/s) against the hydrogen headpressure of 6 PSIG over a period of 38 minutes controlling the reactiontemperature at 80° C. Within 10 minutes of initiation of the monomerfeed the reactor temperature reached 79° C. and the pressure wasincreased to 13 PSIG. Periodically the hydrogen uptake was monitored byclosing the valve to the regulator and timing the period required todrop 5 PSIG. Thus the period in seconds required for the pressure todrop (−1) one PSIG was recorded.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water and 200 ml of cyclohexane.

During the transfer of the unquenched reaction mixture a 10 ml samplewas obtained for analysis. The sample was essentially water white—i.e.colorless and transparent to light—with no settled or suspended solids.The sample was quenched by the addition of a drop of methanol from atransfer pipet. The methanol quench produced hydrogen very slowly butconstantly over a period greater than one hour—with hydrogen appearingto evolve from extremely small particles that only formed upon theinitial quench. Accordingly the catalyst thus formed is surprisinglyvery slow to undergo methanolysis in cyclohexane under the endingconditions of the polymerization. GPC Analysis of the crude quenchedreaction mixtures including the dimer content was as follows: M_(n):702, M_(w): 1091, M_(z): 1489, PD: 1.554, σ_(n)=523, _(n)α₃=1.537—thusthese conditions produce a linear (no branching) anionic chain transferdistribution of exceptionally low asymmetry.

Standard Work-Up and Product Isolation

The two phase product mixture was heated to 65° C. in the wash reactorand then the phases were separated. Phase cuts were easily made at 65°C., and were rapid requiring little settling time. Water and any rag oremulsion was removed through the bottom drain valve. The pH of the washwater removed from the reactor was monitored, the first wash invariably(meaning all previous and subsequent like runs) had pH=14. An additionaldeoxygenated water wash was conducted; the removed water wash phase hada pH 12. The organic phase was then washed with 300 ml of 3 wt % H₂SO₄followed by two 300 ml tap water washes with an ending pH of 7. Thewater washed product mixture was stripped in the wash reactor ofcyclohexane and ethylbenzene by normal distillation while graduallyheating the wash reactor's jacket temperature to 165° C. Thedistillation was deemed complete when the pot temperature reached atemperature above 140° C. The solution was allowed to cool beforecollecting 394.75 g of solution. The solution was then further strippedof ethylbenzene with the use of a wiped film evaporator (WFE, 2″ glassPope Still, operated at 50.0 mmHg vacuum, 140° C., wiper speed 60% offull rate, feeding at 1.0 liters/hr). This first WFE operation produced245.0 g LOXLiH PS distribution having GPC MWD including dimer of M_(n):702, M_(w): 1091, M_(z): 1489, PD: 1.554, σ_(n)=523, _(n)α₃=1.537. Asecond WFE operation (0.1-0.3 mmHg vacuum, 172.5° C., wiper speed 60% offull rate, feeding at 1.0 liters/hr) provided 217.9 g of a LOXLiH PSdistribution having 2.40 GPC area % styrene dimer content and a GPC MWDof M_(n): 821, M_(w): 1152, M_(z): 1505, PD: 1.403, a_(n)=521,_(n)α₃=1.417.

Examples 14 and 15 Representative of Full Scale Monomer Feed Volume forLOXLiH [DMEA⁻]₄Li₆H₂ Catalyst at 80° C. w/ Oligomer MicrostructureAnalysis

Anhydrous cyclohexane, 150 ml of 300 ml (233.7 g) was charged to thereactor at 37° C. under a dry hydrogen (10 PSIG H₂) atmosphere. To thestirred solvent (800 RPM, three pitched blade turbines withConfiguration III above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 2.72 g(0.0305 mol.) N,N-dimethylethanolamine, 140.0 g (1.32 mol) ethylbenzeneand 1.82 g (0.0157 mol) of TMEDA. The charge vessel and transfer line tothe reactor was flushed with a 50 ml portion of anhydrous cyclohexanefrom the total amount above. Next, 22.90 ml (0.0458 mole) 2.0 Mn-butyllithium was transferred through the charge vessel to the reactorfollowed by two 50 ml aliquots of the anhydrous cyclohexane from thetotal amount above. During the organolithium charge agitation speed wasincreased to 1130 RPM and the reactor pressure decreased to 9 PSIG overthe course of the 15 minute charge period. The reactor head space waspurged and vented with 50 PSIG to 0 PSIG with dry H₂ (through asubsurface feedline) three times (slowly venting to keep the contentsfrom foaming out of the reactor) leaving the reactor at 45 PSIG. Thereactor was then heated to 74° C. with the pressuring building to 63PSIG. The heating was conducted with 81° C. oil flowing through thereactor jacket. Upon reaching a reaction temperature of 73° C. thestyrene monomer feed was initiated, feeding 960.4 g g (9.22 mol.) ofstyrene. The styrene was fed through a subsurface feed line (0.02″ IDtip, 1.88 ft/s) against the hydrogen head pressure over a period of 151minutes controlling the reaction temperature at 80° C. Within 10 minutesof initiation of the monomer feed the reactor temperature reached 81° C.and the pressure had dropped to 13 PSIG. The hydrogen regulator was setto maintain a pressure of 16 PSIG. Periodically the hydrogen uptake wasmonitored by closing the valve to the regulator and timing the periodrequired to drop 5 PSIG. Thus the period in seconds required for thepressure to drop (−1) one PSIG was recorded. When this value wasadjusted for estimated reactor headspace, the hydrogen uptake in termsof mole H₂ per mole of styrene feed appeared constant or near constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water. Thus the reaction mixture was quenched with care inthe wash reactor. The above process was repeated as Example 15 with theidentical charges and conditions to within minor run to run variationsin measuring out the reagents and reproducing the conditions except that1020.4 g g (9.80 mol.) of styrene was fed over a period of 160 minutes.As noted above during the added 9 minutes of feed hydrogen uptake andwas reduced somewhat.

During the transfer of the unquenched reaction mixtures (Examples 14 and15) 10 ml samples of the individual reaction mixtures were obtained foranalyses. The samples were essentially water white—i.e. colorless andtransparent to light—with no settled or suspended solids. The sampleswere quenched by the addition of a drop of methanol from a transferpipet. The methanol immediately resulted in the formation and evolutionof hydrogen gas. GPC Analysis of the crude quenched reaction mixturesincluding the dimer content was as follows: Example 14 M_(n): 439,M_(w): 628, M_(z): 886, PD: 1.411, σ_(n)=288, _(n)α₃=2.108; Example 15M_(n): 428, M_(w): 636, M_(z): 979, PD: 1.539, σ_(n)=298, _(n)α₃=2.778.

The standard work-up from above provided 3271 g of solution. Wiped filmevaporation (WFE, 2″ glass Pope Still, operated at 50.0 mmHg vacuum,140° C., wiper speed 60% of full rate, feeding at 1.0 liters/hr)produced 1793 g LOXLiH PS distribution having GPC MWD including dimer ofM_(n): 434, M_(w): 630, M_(z): 934, PD: 1.452, σ_(n)=292, _(n)α₃=2.543.A second WFE operation (0.1-0.3 mmHg vacuum, 172.5° C., wiper speed 60%of full rate, feeding at 1.0 liters/hr) provided 1492 g of a LOXLiH PSdistribution having 2.40 GPC area % styrene dimer content and a GPC MWDof M_(n): 530, M_(w): 731, M_(z): 1150, PD: 1.379, σ_(n)=326,_(n)α₃=3.661. A third WFE operation was performed to obtain the lowmolecular weight oligomers in order to determine the LOXLiH PSdistribution microstructure. Thus a 163.2 g sample of the 1492 g productdistribution recovered from the 2^(nd) WFE operation was stripped ofoligomers (0.13 mmHg vacuum, 199.5° C., wiper speed 85% of full rate,feeding at 2.0 g/min.). This third WFE operation produced 31.24 g of astyrene oligomer mixture having GPC MWD: of M_(n): 310, M_(w): 323,M_(z): 337, PD: 1.043. GC analysis indicated that 99.940% of the chainshad the desired “head to tail” microstructure, with only a trace if anyof chains having the fragmented (FW_(i)−14) microstructure (See FIG. 3).

It should be noted that Examples 14 and 15 are nearly identical exceptthat an additional amount of styrene monomer was employed in Example 15.These Examples utilized impeller configuration III which was more thanadequate for uniform for hydrogen transfer to the condensed phase forExample 14 but proved to be just less than fully adequate for the added60 grams of monomer fed in Example 15. This is reflected in theincreased values of PD_(n), σ_(n) and _(n)α₃ for the MWD of Example 15as compared to Example 14 (Table V). Thus in order to feed more monomerto the same size starting reaction medium a fourth impeller was added tothe agitator shaft spaced as indicated above for Configuration IV.Configuration IV was utilized in Example 20-21 and 24. Example 21 wasidentical to Example 20 except that Example 21 utilized only 25% of thepreferred total monomer feed. This was done in order to explore how themolecular weight distribution evolves over the course of a run. Based onthis experiment the values of PD_(n), and _(n)α₃ decrease as themolecular weight increases indicating that as the feed continues adistribution of less breadth and asymmetry are formed with eachincrement of styrene monomer fed all the while forming incrementallydifferent statistical distributions of dead polymer chains andsimultaneously reforming the LOXLiH catalyst. This combination ofexperiments would indicate that a continuous process operated at steadystate conditions can be utilized to form even more preferred molecularweight distributions of desired low polydispersity, breadth andasymmetry.

Examples 20 and 21 Representative of Full Scale Monomer Feed VolumeLOXLiH [DMEA⁻]₂Li₆H₄ Catalyst at 80° C.

Anhydrous methylcyclohexane, 150 ml of 300 ml (231.0 g) was charged tothe reactor at −5° C. under a dry hydrogen (12 PSIG H₂) atmosphere. Tothe stirred solvent (800 RPM, four pitched blade turbines withConfiguration IV above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 1.00 g(0.0112 mol.) N,N-dimethylethanolamine, 140.0 g (1.32 mol) ethylbenzeneand 2.60 g (0.022 mol) of TMEDA. The charge vessel and transfer line tothe reactor was flushed with a 50 ml portion of anhydrousmethylcyclohexane from the total amount above. Next, 16.81 ml (0.0336mole) 2.0 M n-butyllithium was transferred through the charge vessel tothe reactor followed by two 50 ml aliquots of the anhydrousmethylcyclohexane from the total amount above. During the organolithiumcharge agitation speed was increased to 1130 RPM and the reactorpressure increased to 14 PSIG over the course of the 15 minute chargeperiod. The reactor head space was purged with 50 PSIG with dry H₂(through a subsurface feedline) and venting three times (slowly ventingto keep the contents from foaming out of the reactor) leaving thereactor at 40 PSIG. The reactor was then heated to 70° C. by the timethe reactor temperature had reached 18° C. the pressure had built only 2PSIG to 42 PSIG indicating uptake of hydrogen upon heating. The H₂pressure was increased to 46 PSIG, by the time the reactor reached 72°C. the pressure had built to 60 PSIG. The heating process was conductedwith 81° C. oil flowing through the reactor jacket. Upon reaching 72° C.the styrene monomer feed was initiated, feeding 1042.5 g (10.01 mol.) ofstyrene. The styrene was fed through a subsurface feed line (0.02″ IDtip, 1.88 ft/s) against the hydrogen head pressure over a period of 164minutes controlling the reaction temperature at 80° C. Within 10 minutesof initiation of the monomer feed the reactor temperature reached 80° C.and the pressure had dropped to 32 PSIG. The hydrogen regulator was setto maintain a pressure of 14 PSIG. Periodically the hydrogen uptakemonitored by closing the valve to the regulator and timing the periodrequired to drop 4 PSIG. Thus the period in seconds required for thepressure to drop (−1) one PSIG was recorded. When this value wasadjusted for estimated reactor headspace, the hydrogen uptake in termsof mole H₂ per mole of styrene feed appeared constant or near constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water. Thus the reaction mixture was quenched with care inthe wash reactor. The above process was repeated as Example 21 with theidentical charges and conditions to within minor run to run variationsin measuring out the reagents and reproducing the conditions except that255.0 g (2.45 mol.) of styrene was fed over a period of 40 minutes.

During the transfer of the unquenched reaction mixtures (Examples 20 and21) 10 ml samples of the individual reaction mixtures were obtained foranalyses. The samples were essentially water white—i.e. colorless andtransparent to light—with no settled or suspended solids. The sampleswere quenched by the addition of a drop of methanol from a transferpipet. The methanol immediately resulted in the formation and evolutionof hydrogen gas. GPC Analyses of the crude quenched reaction mixturesincluding the dimer content was as follows: Example 20 M_(n): 466,M_(w): 675, M_(z): 951, PD: 1.409, σ_(n)=312, _(n)α₃=2.033; Example 21M_(n): 408, M_(w): 598, M_(z): 932, PD: 1.559, σ_(n)=278, _(n)α₃=2.993.

The standard work-up from above but conducted at 82° C. provided 1631.5g of solution. Wiped film evaporation (WFE, 2″ glass Pope Still,operated at 50.0 mmHg vacuum, 140° C., wiper speed 60% of full rate,feeding at 1.0 liters/hr) produced 1168 g LOXLiH PS distribution havingGPC MWD including dimer of M_(n): 424, M_(w): 626, M_(z): 979, PD:1.476, σ_(n)=293, _(n)α₃=2.9794. A second WFE operation (0.1-0.3 mmHgvacuum, 172.5° C., wiper speed 60% of full rate, feeding at 1.0liters/hr) provided 946 g of a LOXLiH PS distribution having 1.40 GPCarea % styrene dimer content and a GPC MWD of M_(n): 536, M_(w): 722,M_(z): 1049, PD: 1.379, σ_(n)=326, _(b)α₃=2.912.

Examples 24 Representative of Full Scale Monomer Feed Volume LOXLiH[DMEA⁻]₅Li₁₂H₇ Catalyst at 80° C. w/ Oligomer Microstructure Analysis

Anhydrous methylcyclohexane, 150 ml of 300 ml (231.0 g) was charged tothe reactor at −5° C. under a dry hydrogen (13 PSIG H₂) atmosphere. Tothe stirred solvent (800 RPM, four pitched blade turbines withConfiguration IV above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 2.27 g(0.0255 mol.) N,N-dimethylethanolamine, 140.0 g (1.32 mol) ethylbenzeneand 12.40 g (0.107 mol) of TMEDA. The charge vessel and transfer line tothe reactor was flushed with a 50 ml portion of anhydrousmethylcyclohexane from the total amount above. Next, 30.79 ml (0.0616mole) 2.0 M n-butyllithium was transferred through the charge vessel tothe reactor followed by two 50 ml aliquots of the anhydrousmethylcyclohexane from the total amount above. During the organolithiumcharge agitation speed was increased to 1130 RPM and the reactorpressure increased to 14 PSIG over the course of the 15 minute chargeperiod. The reactor head space was purged and vented with 50 PSIG to 0PSIG with dry H₂ (through a subsurface feedline) three times (slowlyventing to keep the contents from foaming out of the reactor) leavingthe reactor at 41 PSIG. The reactor was then heated to 73° C., by thetime the reactor temperature reached 72° C. the pressure had built to 62PSIG. The heating process was conducted with 81° C. oil flowing throughthe reactor jacket. Upon reaching 73° C. the styrene monomer feed wasinitiated, feeding 1041.0 g (10.00 mol.) of styrene. The styrene was fedthrough a subsurface feed line (0.02″ ID tip, 1.88 ft/s) against thehydrogen head pressure over a period of 164 minutes controlling thereaction temperature at 80° C. Within 10 minutes of initiation of themonomer feed the reactor temperature reached 81° C. and the pressure haddropped to 34 PSIG. The hydrogen regulator was set to maintain apressure of 14 PSIG. Periodically the hydrogen uptake monitored byclosing the valve to the regulator and timing the period required todrop 4 PSIG. Thus the period in seconds required for the pressure todrop (−1) one PSIG was recorded. When this value was adjusted forestimated reactor headspace, the hydrogen uptake in terms of mole H₂ permole of styrene feed appeared constant or near constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (acidic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water. Thus the reaction mixture was quenched with care inthe wash reactor.

During the transfer of the unquenched reaction mixture a 10 ml sample ofthe reaction mixture was obtained for analyses. The sample wasessentially water white—i.e. colorless and transparent to light—with nosettled or suspended solids. The sample was quenched by the addition ofa drop of methanol from a transfer pipet. The methanol quenchimmediately resulted in the formation and evolution of hydrogen gas. GPCAnalyses of the crude quenched reaction mixture including the dimercontent was as follows: M_(n): 466, M_(w): 675, M_(z): 951, PD: 1.409,σ_(n)=312, _(n)α₃=2.033.

The standard work-up from above but conducted at 82° C. provided 1312.9g of solution. Wiped film evaporation (WFE, 2″ glass Pope Still,operated at 50.0 mmHg vacuum, 140° C., wiper speed 60% of full rate,feeding at 1.0 liters/hr) produced 966.2 g LOXLiH PS distribution havingGPC MWD including dimer of M_(n): 477, M_(w): 685, M_(z): 961, PD:1.436, σ_(n)=315, _(n)α₃=2.032. A second WFE operation (0.1-0.3 mmHgvacuum, 172.5° C., wiper speed 60% of full rate, feeding at 1.0liters/hr) provided 828.4 g of a LOXLiH PS distribution having 1.2 GPCarea % styrene dimer content and a GPC MWD of M_(n): 575, M_(w): 753,M_(z): 933, PD: 1.310, σ_(n)=320, _(n)α₃=1.933. A third WFE operationwas performed to obtain the low molecular weight oligomers in order todetermine the LOXLiH PS distribution microstructure. Thus a 106.2 gsample of the 966.2 g product distribution recovered from the 2^(nd) WFEoperation was stripped of oligomers 0.1 mmHg vacuum, 199.5° C., wiperspeed 85% of full rate, feeding at 2.0 g/min.). This third WFE operationproduced 33.17 g of a styrene oligomer mixture having GPC MWD: of M_(n):372, M_(w): 398, M_(z): 426, PD: 1.069. GC analysis indicated that99.82% of the chains had the desired “head to tail” microstructure, withonly a trace id any of the chains having the fragmented (FW_(i)−14)microstructure (See FIG. 4).

Upon completion of the series of LOXLiH runs (Examples 29-35) theautoclave reactor was rinsed with standard drum grade (not anhydrous)cyclohexane, purged well with nitrogen and then opened for inspection.The heated reactor walls and the cold surfaces (i.e. cooling coils,agitator assembly, dip leg, monomer feed-line and thermowell) for allintents and purposes were free of all solids.

Examples 25-29

The experimental details of Examples 25-29 (reaction conditions, reagentcharges, and initial as well as final catalyst concentration), scale-upparameters (relative feeds and relative hourly feed rates) and results(polymer molecular weight distribution as determined by GPC and polymeryield) are presented in tabular form in Table VII. As was stated aboveis reiterated here, it should be clear that the LOXSH catalyst andpolymerization reaction conditions of this invention provide countlesscombinations of the reagents from which they are synthesized and thereaction parameters under which a process is conducted. These Examples25-29 include bimetallic catalyst involving other saline hydrides. ThusExamples 25-27 entail the use of potassium hydride in forming the LOXKHcatalyst and Examples 28-29 entail formation of LOXMgH₂ catalyst usingan organomagnesium reagent. Examples 26, 28 and 29 are described ingreater detail.

It should be noted that GC analyses of the four to six most volatilestyrene oligomers of the LOXMgH₂ PS compositions thus produced (Examples28-29) demonstrated 99.2% linear “head to tail” polymer microstructureessentially free of any fragmentation polymerization impurities orco-product distributions. Statistical models (Beta PDF) of thesedistributions indicate that about 99.982 mole % of the styrene repeatingunits have either 2° (methylene) or 3° (methine) benzylic carbon atoms.Put in another way, these LOXMgH₂ PS compositions have no more than 185ppm quaternary carbon “tail to head to tail” linkages. Analyses of theLOXKH produced oligomers showed very high levels—8 to 12% of thediscrete polymer chains—of the composition with a single quaternarycarbon head “tail to head to tail” linkages. Thus based on statisticalmodels of these compositions (Beta PDF) the LOXKH compositions can haveless than 99.725 mole % of the styrene repeating units with either a 2°(methylene) or a 3° (methine) benzylic carbon atoms. This means thatthese compositions can have greater than 2750 ppm quaternary carbon“tail to head to tail” linkages rendering them less preferredcompositions for certain applications.

Surprisingly even the composition of Example 27 produced from a LOXKHcatalyst having a Li:K ratio of 15:1 produced a composition with greaterthan 8 wt % of the chains with the undesired single quaternary carbon“tail to head to tail” linkages. It is assumed in part based on resultsto be presented in Table VII, that a catalyst formed from one part DMEAHto 2 parts of a Group I metal (M⁺) exist as an aggregate with theformula [DMEA⁻]₄M₈H₄. Based on this assumption the catalysts of Example27 (15:1 Li:K) could be comprised of 1 aggregate having the formula[DMEA⁻]₄Li₈H₄ and one aggregate having the formula [DMEA⁻]₄Li₇KH₄. Thecatalyst of Example 25 (3:1 Li:K) may well be an aggregate or aggregateshaving the formula [DMEA⁻]₄Li₆K₂H₄ and the catalyst of Example 26 (7:1Li:K) may be an aggregate having the formula [DMEA⁻]₄Li₇KH₄. Whereinwith each of these aggregate catalyst systems, the most active hydridespecies is the KH in terms of initiation and consequently in terms offormation of less desired polymer microstructure—as these three Examples(25, 26 and 27) provided just like all other potassium based catalystsystems.

In comparison and contrast to LOXKH, Examples 28 and 29 which arerepresentative of LOXMgH₂ aggregate catalyst systems, it would appearthat a LOXLiH aggregate catalyst is more active than the LOXMgH₂. ForExample 28 the stoichiometric ratio of DMEAH to n-butyllithium todibutylmagnesium is such that if one single aggregate were formed itwould have the empirical formula [DMEA⁻]₂₁Li₂₈Mg₄H₁₅, and thus thereshould or at least could exist both LiH and MgH₂ active species. It isanticipated that several different aggregates form and some of which maybe free of magnesium and hence a form of LiH as the active reagentshould exist in the catalyst composition. In contrast, Example 29 then-butyllithium and dibutylmagnesium charges were such as to consume allof the lithium alkyl radicals (butyllithium groups) leaving onlymagnesium alkyl radicals (dibutylmagnesium groups). The stoichiometryand anticipated empirical formula of Example 29 is [DMEA⁻]₄Li₄MgH₂ andthus no explicit form of LiH should exist.

In that Example 28 could be run at a significantly lower hydrogenpressure than Example 29 to obtain similar product MWDs, it is surmisedthat an all lithium catalyst aggregate is likely present and is moreactive as a catalyst for the hydrogen mediated saline hydride initiatedpolymerization process then a catalyst aggregate comprising some amountof magnesium hydride. Again, Example 29 the catalyst was formed suchthat no active LiH would be present (i.e. the moles of DMEAH was inexcess of the moles of organolithium charged). This catalyst system wasvery effective but required a much higher H₂ pressure than Example 28.Given the demands of a commercial reactor (challenges in maintaining aconstant pressure and the simple amount of back pressure needed for aproper seal) this need for a modestly higher H₂ pressure is deemed asfortuitous advantage over the LOXLiH catalyst (Examples 1-24) and themixed LOXLiH LOXMgH₂ catalyst of Example 28.

Formation of a “[DMEA⁻]₂LiK.2TMEDA Stock Solution for Examples 25-27

Unlike potassium tert-butoxide which is easily solubilized by 2 to 5moles of TMEDA into hydrocarbon solvents, the potassium alkoxide formedfrom N,N-dimethylethanolamine, [DMEA⁻]K, appears to be poorly solubleeven with TMEDA added. However a mixed metal alkoxide formed frompotassium hydride, n-butyllithium and DMEAH was easily dissolved inethylbenzene. Thus a 6.12 wt % homogenous 206.71 g stock solution ofTMEDA complexed mixed metal aminoalkoxide “[DMEA⁻]₂LiK.2TMEDA” solutionin ethylbenzene was prepared under a nitrogen atmosphere in 182.5 (1.72moles anhydrous ethylbenzene from 1.10 g (0.274) dry fresh KH, 4.90 g(0.0550 mole) DMEAH, 6.51 (0.560 mole) TMEDA, and 15.12 ml (0.0302moles) 2.0 M n-butyllithium in cyclohexane. This was accomplished bycharging 3.67 g of 30 wt % KH in mineral oil to a previously weighedoven dried 500 ml borosilicate glass bottle and glass coated stirrer barplaced on to a stirrer hot plate in a nitrogen purged glovebox. Thepotassium hydride suspension was then washed and decanted three timeswith 30 ml of anhydrous n-pentane. After drying to a constant weightunder a stream of dry nitrogen, 182.46 g of ethylbenzene, 6.51 g TMEDA(/99.5%) and 4.90 g of DMEAH (/99.5%, added in portions as H₂ evolved)were then charged. The resulting heterogeneous solution was gentlywarmed to 50° C. and n-butyllithium was added slowly until a homogenoussolution was formed. A 10 mole % excess of n-butyllithium was needed toproduce a homogenous solution with a persistent faint red colorindicating the presence of other protic species. One drop of DMEAH wasadded to quench the red color and upon cooling to room temperature thestock solution remained homogenous. Aliquots of this 6.12 wt %homogenous stock solution containing the desired amount of potassiumions were then used in forming the reaction mixture of Examples 25-27.

Examples 26 Representative of LOXKH [DMEA⁻]₄L₁₇KH₄ Catalyst at 80° C. w/Oligomer Microstructure Analysis

Anhydrous cyclohexane, 150 ml of 300 ml (233.7 g) was charged to thereactor at 37° C. under a dry hydrogen (10 PSIG H₂) atmosphere. To thestirred solvent (800 RPM, three pitched blade turbines withConfiguration III above) was charged through the charge vessel viapositive nitrogen pressure, 51.68 g of the 6.12 wt % homogenous asolution described above was combined with an additional 1.23 g (0.0138mol.) N,N-dimethylethanolamine and 1.63 g (0.0140 mol) of TMEDAdissolved in 50.0 ml anhydrous cyclohexane. The charge vessel andtransfer line to the reactor was flushed with a 50 ml portion ofanhydrous cyclohexane from the total amount above. Next, 20.66 ml(0.0413 mole) 2.0 M n-butyllithium diluted with 42.71 g (0.403) ofanhydrous EB was transferred through the charge vessel to the reactorfollowed by two 50 ml aliquots of the anhydrous cyclohexane from thetotal amount above. During the organolithium charge agitation speed wasincreased to 1130 RPM and the reactor pressure decreased to 8 PSIG overthe course of the 18 minute charge period. The reactor head space waspurged and vented with 50 PSIG with dry H₂ (through a subsurfacefeedline) three times (slowly venting to keep the contents from foamingout of the reactor) leaving the reactor at 41 PSIG. The reactor was thenheated to 75° C. with the pressuring building to 62 PSIG. The heatingwas conducted with 81° C. oil on the reactor jacket. Upon reaching 75°C. the styrene monomer feed was initiated, feeding 996.9 g (9.57 mol.)of styrene. The styrene was fed through a subsurface feed line (0.02″ IDtip, 1.88 ft/s) against the hydrogen head pressure over a period of 156minutes controlling the reaction temperature at 81.5° C. Within 10minutes of initiation of the monomer feed the reactor temperaturereached 82° C. and the pressure had dropped to 47 PSIG. The hydrogenregulator was set to maintain a pressure of 22 PSIG. Periodically thehydrogen uptake was monitored by closing the valve to the regulator andtiming the period required to drop 5 PSIG. Thus the period in secondsrequired for the pressure to drop (−1) one PSIG was recorded. When thisvalue was adjusted for estimated reactor headspace, the hydrogen uptakein terms of mole H₂ per mole of styrene feed appeared fall off somewhatduring the course of the monomer feed which indicated that ethylbenzenein addition to hydrogen behaves as a chain transfer agent with thiscatalyst composition.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water. During the transfer of the unquenched reactionmixture a 10 ml sample of the reaction mixture was obtained foranalyses. The sample was red in color and transparent to light with nosettled or suspended solids. The sample was quenched by the addition ofa drop of methanol from a transfer pipet. The methanol quenchimmediately resulted in the formation and evolution of hydrogen gas.Based on GPC analyses of the crude quenched reaction mixtures includingthe dimer content was as follows: M_(n): 688, M_(w): 1051, M_(z): 1461,PD: 1.527, σ_(n)=500, _(n)α₃=1.725.

The standard work-up from above but conducted at 82° C. provided 1159.5g of solution. Wiped film evaporation (WFE, 2″ glass Pope Still,operated at 50.0 mmHg vacuum, 140° C., wiper speed 60% of full rate,feeding at 1.0 liters/hr) produced 935 g LOXLKH PS distribution havingGPC MWD including dimer of M_(n): 689, M_(w): 1051, M_(z): 1461, PD:1.527, σ_(n)=500, _(n)α₃=1.725. A second WFE operation (0.1-0.3 mmHgvacuum, 172.5° C., wiper speed 60% of full rate, feeding at 1.0liters/hr) provided 845 g of a LOXKH PS distribution having 0.48 GPCarea % styrene dimer content and a GPC MWD of M_(n): 765, M_(w): 1099,M_(z): 1486, PD: 1.437, σ_(n)=505, _(n)α₃=1.667. A third WFE operationwas performed to obtain the low molecular weight oligomers in order todetermine the LOXKH PS distribution microstructure. Thus a 150.2 gsample of the 845 g product distribution recovered from the 2^(nd) WFEoperation was stripped of oligomers 0.1 mmHg vacuum, 199.5° C., wiperspeed 85% of full rate, feeding at 2.0 g/min.). This third WFE operationproduced 18.94 g of a styrene oligomer mixture having GPC MWD: of M_(n):34, M_(w): 371, M_(z): 400, PD: 1.077. GC analysis indicated that 89.53%of the chains had the desired “head to tail” microstructure, with 0.78%of the chains having the fragmented (FW_(i)−14) microstructure and thebalance of the chains possess the less desired sing quaternary “tail tohead to tail” linkage in the discrete polymer chains (See FIG. 6). Thegas chromatogram in FIG. 6 demonstrates the oligomer microstructurepurity: 89.53% “Head to Tail” Microstructure; 9.7% of oligomers w/ onequaternary “tail to head to tail” linkage; and 0.78% (FW_(i)−14)fragmentation oligomers.

Examples 28 Representative of Full Monomer Feed for LOXMgH₂[DMEA⁻]₂₁Li₂₈Mg₄H₁₅ Catalyst at 80° C.

Anhydrous methylcyclohexane, 175 ml of 375 ml (288.8 g) was charged tothe reactor at −5° C. under a dry hydrogen (13 PSIG H₂) atmosphere. Tothe stirred solvent (800 RPM, four pitched blade turbines withConfiguration VI above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 3.32 g(0.0372 mol.) N,N-dimethylethanolamine, 30.0 g (0.28 mol) ethylbenzeneand 6.51 g (0.056 mol) of TMEDA. The charge vessel and transfer line tothe reactor was flushed with a 50 ml portion of anhydrousmethylcyclohexane from the total amount above. Next, 24.50 ml (0.0490mole) 2.0 M n-butyllithium in cyclohexane dissolved in 80 g (0.75 mole)was transferred through the charge vessel to the reactor followed by two50 ml aliquots of the anhydrous methylcyclohexane from the total amountabove. Then 7.00 ml of 1.0 M dibutylmagnesium (0.007 mole) in heptanedissolved in 30.0 g (0.28 mole) ethylbenzene was charged and transferredthrough the charge vessel to the reactor followed by a 50 ml aliquot ofthe anhydrous methylcyclohexane from the total amount above. During theorganolithium/organomagnesium charge agitation speed was increased to1130 RPM and the reactor pressure increased to 16 PSIG over the courseof the 15 minute charge period. The reactor head space was purged andvented with 50 PSIG with dry H₂ (through a subsurface feedline) threetimes (slowly venting to keep the contents from foaming out of thereactor) leaving the reactor at 46 PSIG and −3.4° C. The reactor wasthen heated to 40° C. by the time (45 min.) the reactor temperaturereached 40° C. the pressure had built to 55 PSIG. The reactor was ventedto 46 PSIG and heating continued. After an additional 15 minutes ofheating the reactor reached 67° C. and the pressure was set to 63 PSIG.The heating process was conducted with 81° C. oil on the reactor jacket.Upon reaching 72° C. and 64 PSIG the styrene monomer feed was initiated,feeding 1009.0 g (9.69 mol.) of styrene. The styrene was fed through asubsurface feed line (0.02″ ID tip, 1.88 ft/s) against the hydrogen headpressure over a period of 159 minutes controlling the reactiontemperature at 82° C. Within 10 minutes of initiation of the monomerfeed the reactor temperature reached 80° C. and the pressure had droppedto 36 PSIG. The hydrogen regulator was set to maintain a pressure of 14PSIG for the next 40 minutes of feed. After a total of 60 minutes offeeding monomer, the hydrogen pressure was set to 11 PSIG. Periodicallythe hydrogen uptake was monitored by closing the valve to the regulatorand timing the period required to drop 4 PSIG. Thus the period inseconds required for the pressure to drop (−1) one PSIG was recorded.When this value was adjusted for estimated reactor headspace, thehydrogen uptake in terms of mole H₂ per mole of styrene feed appearednear constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (acidic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml of 3 wt %H₂SO₄. During the transfer of the unquenched reaction mixture a 10 mlsample of the reaction mixture was obtained for analyses. The sample waslight yellow in color with no solids observed. The sample was quenchedby the addition of a drop of methanol from a transfer pipet. Themethanol quench immediately resulted in quenching of the yellow colorand the formation and evolution of hydrogen gas. GPC Analyses of thecrude quenched reaction mixtures including the dimer content was asfollows: M_(n): 504, M_(w): 773, M_(z): 1180, PD: 1.534, σ_(n)=368,_(n)α₃=2.538.

The two phase product mixture was heated to 82° C. in the wash reactorand then the phases were separated. Phase cuts were easily made at 82°C., and were rapid requiring little settling time. The organic phase wasthen washed with 4×300 ml of tap water until an ending pH of 7 wasachieved. The standard solvent strip from the above standard productisolation provided 1561.8 g of solution. Wiped film evaporation (WFE, 2″glass Pope Still, operated at 50.0 mmHg vacuum, 140° C., wiper speed 60%of full rate, feeding at 1.0 liters/hr) produced 962 g LOXMgH₂ PSdistribution having GPC MWD including dimer of M_(n): 511, M_(w): 780,M_(z): 1187, PD: 1.526, σ_(n)=371, _(n)α₃=2.530. A second WFE operation(0.1-0.3 mmHg vacuum, 172.5° C., wiper speed 60% of full rate, feedingat 1.0 liters/hr) provided 828.4 g of a LOXMgH₂ PS distribution having1.1 GPC area % styrene dimer content and a GPC MWD of M_(n): 622, M_(w):853, M_(z): 1207, PD: 1.371, σ_(n)=379, _(n)α₃=2.417.

Examples 29 Representative of 50% Monomer Feed Volume for LOXMgH₂[DMEA⁻]₄Li₄MgH₂ Catalyst at 80° C. w/ Oligomer Microstructure Analysis

Anhydrous methylcyclohexane, 175 ml of 375 ml (288.8 g) was charged tothe reactor at −5° C. under a dry hydrogen (12 PSIG H₂) atmosphere. Tothe stirred solvent (800 RPM, four pitched blade turbines withConfiguration VI above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 5.00 g(0.0561 mol.) N,N-dimethylethanolamine, 30.0 g (0.28 mol) ethylbenzeneand 8.15 g (0.056 mol) of TMEDA. The charge vessel and transfer line tothe reactor was flushed with a 50 ml portion of anhydrousmethylcyclohexane from the total amount above. Next, 28.05 ml (0.0561mole) 2.0 M n-butyllithium in cyclohexane dissolved in 80 g (0.75 mole)was transferred through the charge vessel to the reactor followed by two50 ml aliquots of the anhydrous methylcyclohexane from the total amountabove. Then 14.00 ml of 1.0 M dibutylmagnesium (0.014 mole) in heptanedissolved in 30.0 g (0.28 mole) ethylbenzene was charged and transferredthrough the charge vessel to the reactor followed by a 50 ml aliquot ofthe anhydrous methylcyclohexane from the total amount above. During theorganolithium/organomagnesium charge agitation speed was increased to1130 RPM and the reactor pressure increased to 17 PSIG over the courseof the 16 minute charge period. The reactor head space was vented to 0PSIG and then pressured to 65 PSIG with dry H₂ (through a subsurfacefeedline) and venting three times (slowly venting to keep the contentsfrom foaming out of the reactor) leaving the reactor at 44 PSIG and−4.4° C. The reactor was then heated to 71° C. over 120 minutes with theheating process conducted with 81° C. oil on the reactor jacket. Uponreaching 71° C. and 61 PSIG the styrene monomer feed was initiated,feeding 509.0 g (4.89 mol.) of styrene. The styrene was fed through asubsurface feed line (0.02″ ID tip, 1.88 ft/s) against the hydrogen headpressure over a period of 80 minutes controlling the reactiontemperature at 81° C. Within 10 minutes of initiation of the monomerfeed the reactor temperature reached 80° C. and the pressure had droppedto 49 PSIG. (However it is pointed out that hydrogen consumption asevidence in a drop in pressure was delayed by about 0.25 to 0.75 minuteswhen compared to a LOXLiH run.) The hydrogen regulator was set tomaintain a pressure of 46 PSIG for the next 40 minutes of feed. Aftertotal of 60 minutes of feeding monomer the hydrogen pressure was thencontrolled at 65 PSIG. Periodically the hydrogen uptake was monitored byclosing the valve to the regulator and timing the period required todrop 4 PSIG. Thus the period in seconds required for the pressure todrop (−1) one PSIG was recorded. When this value was adjusted forestimated reactor headspace, the hydrogen uptake in terms of mole H₂ permole of styrene feed appeared near constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml of 3 wt %H₂SO₄. During the transfer of the unquenched reaction mixture a 10 mlsample of the reaction mixture was obtained for analyses. The sample waslight yellow in color with some large particles that settled. The samplewas quenched by the addition of a drop of methanol from a transferpipet. The methanol quench immediately resulted in quenching of theyellow color and the formation and evolution of hydrogen gas. GPCAnalyses of the crude quenched reaction mixtures including the dimercontent was as follows: M_(n): 481, M_(w): 713, M_(z): 1008, PD: 1.482,σ_(n)=334, _(n)α₃=1.969.

The work-up and strip procedure of Example 28 yielded 729.9 g ofsolution. Wiped film evaporation (WFE, 2″ glass Pope Still, operated at50.0 mmHg vacuum, 140° C., wiper speed 60% of full rate, feeding at 1.0liters/hr) produced 492 g LOXMgH₂ PS distribution having GPC MWDincluding dimer of M_(n): 485, M_(w): 718, M_(z): 1018, PD: 1.480,σ_(n)=336, _(n)α₃=2.000. A second WFE operation (0.1-0.3 mmHg vacuum,172.5° C., wiper speed 60% of full rate, feeding at 1.0 liters/hr)provided 427 g of a LOXMgH₂ PS distribution having 1.1 GPC area %styrene dimer content and a GPC MWD of M_(n): 593, M_(w): 805, M_(z):1116, PD: 1.358, σ_(n)=355, _(n)α₃=2.256. A third WFE operation wasperformed to obtain the low molecular weight oligomers in order todetermine the LOXMgH₂ PS distribution microstructure. Thus a 94.5 gsample of the 492 g product distribution recovered from the 2^(nd) WFEoperation was stripped of oligomers (0.12 mmHg vacuum, 199.5° C., wiperspeed 85% of full rate, feeding at 2.0 g/min.). This third WFE operationproduced 15.73 g of a styrene oligomer mixture having GPC MWD: of M_(n):314, M_(w): 329, M_(z): 344, PD: 1.049. GC analysis indicated that99.21% of the chains had the desired “head to tail” microstructure, freeof chains having the fragmented (FW_(i)−14) microstructure with tracequantities of oligomers initiated with a butyl group (See FIG. 8). Thegas chromatogram in FIG. 8 demonstrates the oligomer microstructurepurity: 99.21% “Head to Tail” Microstructure; 0.0% fragmentationoligomers; and a trace of [n-butyl]MgH initiated styrene oligomers w/0.0% TEA ethyl end group incorporation. The slight delay in hydrogenconsumption observed and the presence of trace polystyrene distributioninitiated with a butyl group might suggest that formation of a magnesiumhydride composition is more completely achieved after alkylation ofstyrene by the residual butylmagnesium radical in the catalystcomposition. This might suggest that a benzylmagnesium or benzylmagnesite reagent is more readily reduced by hydrogen than analiphaticmagnesium or aliphatic magnesite reagent.

Upon completion of this series of LOXMgH₂ runs (Examples 28 and 29) theautoclave reactor was rinsed with standard drum grade (not anhydrous)cyclohexane, purged well with nitrogen and then opened for inspection.The heated reactor walls and the cold surfaces (i.e. cooling coils,agitator assembly, dip leg, monomer feed-line and thermowell) forcovered in scaly white solids. A tap water rinse of the solids off thereactor surfaces produced a pH=11 rinsate. Analysis (ICP) indicated thatthe scaly solids were comprised of lithium and magnesium salts, 84.0milligrams as LiOH (3.51 mmoles Li or 3.34% of total lithium) and 0.24milligrams (0.004 mmole Mg or 0.02% of total magnesium) as Mg(OH)₂.Between the two runs 105.1 mmoles of lithium and 21.02 mmoles ofmagnesium had been charged, thus the solid residue represents only asmall percentage of the lithium and essentially a trace of the magnesiumcharged.

Examples 30-32

The experimental details of Examples 30-32 (reaction conditions, reagentcharges, and initial as well as final catalyst concentration), scale-upparameters (relative feeds and relative hourly feed rates) and results(polymer molecular weight distribution as determined by GPC and polymeryield) are presented in tabular form in Table VIII. Examples 30-32entail the formation of other LOXLiH catalyst and processes where thecomplexing ligand is either lithium methoxyethoxide [MEOE⁻]Li⁺ orlithium 2-N,N-dimethylaminoethoxyethoxide [DMAEOE⁻]Li⁺. Example 30demonstrates that a hydrocarbon soluble lithium hydride reagent orcatalyst having the empirical formula of [MEOE⁻]₄Li₈H₄.4TMEDA can beformed from 2-methoxyethanol [MEOEH], n-butylithium in the presence ofTMEDA under a hydrogen atmosphere. Example 30 also demonstrates thatthis catalyst system will initiate polymerization of styrene monomer,however the hydrogen mediated or chain transfer process is inefficientunder the conditions of the Example producing only 0.86 moles of polymerchains per mole of complexed lithium hydride. This might imply that itis necessary to have an amine functional group present on the lithiumalkoxide complexing agent of the catalyst, if the catalyst is to promoteor facilitate the hydrogen chain transfer reaction involving the livingpoly(styryl)lithium species. It is to be noted that hydrocarbon solublelithium hydride compositions having the empirical formula [MEOE⁻]₄Li₁₂H₈would have very high hydride content—2.06 wt % hydride—for a hydrocarbonsoluble form of LiH. Likewise a composition with empirical formula[MEOE⁻]₄Li₈H₄ would have a high hydride content—1.12 wt % hydride.

For Examples 31 and 322-N,N-dimethylaminoethoxyethanol [DMAEOEH] wasused to form the hydride reagent or catalyst species. The reagent chargeused in Example 31 was such that a catalyst having the empirical formula[DMAEOE⁻]₄Li₈H₁₄.4TMEDA would be formed. However it was clear from theoutset based on little evidence of hydrogen uptake that little catalystformed. It is surmised that the TMEDA facilitated the decomposition ofthe [DMAEOE⁻]Li⁺ species by n-butyllithium. Thus this catalyst under theconditions of the Example produced a very high molecular weight(M_(w)=183,233) polystyrene composition having a very broad and highlyasymmetric distribution. It is surmised that the TMEDA facilitated thedecomposition of the [DMAEOE⁻]Li⁺ species by n-butyllithium. The reagentcharge used in Example 32 was such that a catalyst having the empiricalformula [DMAEOE⁻]₄Li₆H₂ free of TMEDA would be formed. Additionally thecatalyst was initially formed at −5° C. Under the reaction conditions ofExample 32 the desired catalyst formed and at least initially hadactivity comparable to that of catalysts formed from DMAEH, however thecatalyst activity dropped precipitously during the styrene monomer feedresulting the formation of a high molecular weight tail as indicated byan M_(z)=139,795 with an asymmetry of 34.4. It is surmised that underthe temperature conditions of the reaction decomposition of the catalystresulted. The decomposition of [DMAEOE⁻]Li⁺ whether during catalystformation or during the polymerization process is believed to entailmetalation alpha to the dimethylamino function followed by eliminationof a di-lithium alkoxide of ethylene glycol and formation ofvinyl-dimethylamine (an enamine) as shown below. Thus this ligand andany other ligand susceptible to such possible degradation processes areless preferred to DMEAH for forming catalysts for hydrogen mediatedsaline hydride initiated polymerization processes involving amonometallic lithium catalyst.

Example 30 Representative Pf LOXLiH [MEOE⁻]₄Li₈H₄.4TMEDA Catalyst Formedfrom 2-Methoxyethanol

Anhydrous cyclohexane, 400 ml of 550 ml (428.5 g) was charged to thereactor at 20° C. under a dry hydrogen (0 PSIG H₂) atmosphere. To thestirred solvent (800 RPM, three pitched blade turbines withConfiguration III above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 2.10 g(0.0276 mol.) 2-methoxymethanol, 15.0 g (0.14 mol) ethylbenzene and 3.35g (0.029 mol) of TMEDA. The charge vessel and transfer line to thereactor was flushed with a 50 ml portion of anhydrous cyclohexane fromthe total amount above. Next, 28.77 ml (0.0575 mole) 2.0 Mn-butyllithium in cyclohexane dissolved in 80 g (0.75 mole) wastransferred through the charge vessel to the reactor over 15 minutesfollowed by two 50 ml aliquots of the anhydrous cyclohexane from thetotal amount above. During the organolithium charge agitation speed wasincreased to 1130 RPM and the reactor pressure decreased to −4 PSIG andthe temperature increased to 22° C. indicating the consumption of H₂.The reactor head space was then purged and vented with 50 PSIG to 0 PSIGdry H₂ (through a subsurface feedline) three times (slowly venting tokeep the contents from foaming out of the reactor) leaving the reactorat 35 PSIG. The reactor was then heated to 73° C. over 60 minutes withthe heating process conducted with 81° C. oil flowing through thereactor jacket. Upon reaching 73° C. and 51 PSIG the styrene monomerfeed was initiated, feeding 160.0 g (1.54 mol.) of styrene. The styrenewas fed through a subsurface feed line (0.02″ ID tip, 1.35 ft/s) againstthe hydrogen head pressure over a period of 35 minutes controlling thereaction temperature at 80° C. Within 10 minutes of initiation of themonomer feed the reactor temperature had only reached 78° C. and thepressure had increased to 52 PSIG. The valve to hydrogen regulator waskept closed and the pressure increased as the head space was compressedby the styrene monomer feed. After total of 35 minutes of feeding thehydrogen pressure had reached 55 PSIG.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water. During the transfer of the unquenched reactionmixture a 10 ml sample of the reaction mixture was obtained. The samplewas colorless and transparent to light with no settled or suspendedsolids. The sample was quenched by the addition of a drop of methanolfrom a transfer pipet. The methanol quench immediately resulted in theformation and evolution of hydrogen gas.

The standard work-up and solvent strip from above except that thedistillation was deemed complete when no more ethylbenzene could betaken over head with a nitrogen sparge of the headspace. The resultingresin was transferred through the bottom drain valve to a previouslyweighed metal tray lined with aluminum foil. The resin was then furtherstripped of ethylbenzene in a vacuum oven which was gradually heatedfrom 100° C. to 165° C. with the vacuum gradually increased from 50.0mmHg to 1.0 mmHg vacuum. Upon cooling the resulting brittle colorlessresin was sampled and analyzed by GPC: M_(n): 6179, M_(w): 14,450,M_(z): 22,964, PD: 1.578, σ_(n)=7192, _(n)α₃=2.338.

Example 32 Representative Pf LOXLiH [DMAEOE⁻]₄Li₆H₂ Catalyst Formed from2-N,N-Dimethylaminoethoxyethanol

Anhydrous methylcyclohexane, 150 ml of 300 ml (231.0 g) was charged tothe reactor at −5° C. under a dry hydrogen (0 PSIG H₂) atmosphere. Tothe stirred solvent (800 RPM, three pitched blade turbines withConfiguration III above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 4.00 g(0.0300 mol.) 2-N,N-Dimethylaminoethoxyethanol and 16.0 g (0.14 mol)ethylbenzene. The charge vessel and transfer line to the reactor wasflushed with a 50 ml portion of anhydrous methylcyclohexane from thetotal amount above. Next, 22.54 ml (0.0451 mole) 2.0 M n-butyllithium incyclohexane dissolved in 120 g (1.13 mole) was transferred through thecharge vessel to the reactor over 15 minutes followed by two 50 mlaliquots of the anhydrous methylcyclohexane from the total amount above.During the organolithium charge agitation speed was increased to 1130RPM and the reactor pressure neither increased nor decreased. Thereactor head space was then pressured to 50 PSIG with dry H₂ (through asubsurface feedline) and vented three times (slowly venting to keep thecontents from foaming out of the reactor) leaving the reactor at 36PSIG. The reactor was then heated to 73° C. over 60 minutes with theheating process conducted with 81° C. oil on the reactor jacket. Uponreaching 72° C. and 59 PSIG the styrene monomer feed was initiated,feeding 131.1 g (1.26 mol.) of styrene. The styrene was fed through asubsurface feed line (0.02″ ID tip, 1.35 ft/s) against the hydrogen headpressure over a period of 29 minutes controlling the reactiontemperature at 80° C. Within 10 minutes of initiation of the monomerfeed the reactor temperature had reached 82° C. and the pressure haddropped to 52 PSIG. The hydrogen regulator was set to 36 PSIG. Duringthe first 10-15 minutes of the styrene monomer feed the process appearedto run comparable to a catalyst system formed from DMEA. However it wasquite apparent that by 20 minutes the uptake of hydrogen was quicklydiminishing.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (acidic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water. During the transfer of the unquenched reactionmixture a 10 ml sample of the reaction mixture was obtained. The samplewas colorless and transparent to light with no settled or suspendedsolids. The sample was quenched by the addition of a drop of methanolfrom a transfer pipet. The methanol quench immediately resulted in theformation and evolution of hydrogen gas.

The standard work-up and solvent strip from above except that thedistillation was deemed complete when no more ethylbenzene could betaken over head with a nitrogen sparge of the headspace. The resultingresin was transferred through the bottom drain valve to a previouslyweighed metal tray lined with aluminum foil. The resin was then furtherstripped of ethylbenzene in a vacuum oven which was gradually heatedfrom 100° C. to 165° C. with the vacuum gradually increased from 50.0mmHg to 1.0 mmHg vacuum. Upon cooling the resulting brittle colorlessresin was sampled and analyzed by GPC: M_(n): 745, M_(w): 23,605, M_(z):139,795, PD: 5.922, σ_(n)=4127, _(n)α₃=34.431.

Examples 33-37

The experimental details of Examples 33-37 (reaction conditions, reagentcharges, and initial as well as final catalyst concentration), scale-upparameters (relative feeds and relative hourly feed rates) and results(polymer molecular weight distribution as determined by GPC and polymeryield) are also presented in tabular form in Table VIII. These Examples(33-37) were by design conducted under a hydrocarbon atmosphere withlittle if any hydrogen present. The intent of these Examples is todemonstrate the following four points: (1) the LOXLiH catalyst of thisinvention initiate polymerization of a monomer such as styrene; (2) theresulting M_(n) molecular weight of these Examples provide someexperimental evidence for the actual composition of the LOXLiH catalystaggregates formed; (3) demonstrate that the added promotor TMEDA does infact play a role in defining catalyst activity; and (4) that hydrogen byits absence in these Examples, clearly and unequivocally has the amazingand surprising effect of mediating and perhaps even further activatingthe saline hydride initiated polymerization processes of this invention.

Thus Example 33 which utilized a catalyst having the empirical formula[DMEA⁻]₂Li₃H in a LiH:styrene ratio of 1:31.9 (M_(n) calc=3316) providedan saline hydride initiated polystyrene composition with M_(n)=6707 witha % Efficiency of 50%. Assuming no chain transfer from ethylbenzene,this would imply that only one in two LiH's are available in anaggregate to initiate polymerization and would indicate that the actualcatalytic or initiating species has the chemical formula [DMEA⁻]₄Li₆H₂.In comparison, Example 34 which employed the same catalyst system buthad present 1 mole of TMEDA per mole of lithium metal, produced a salinehydride initiated polystyrene composition with M_(n)=5084. Thus thischarge of TMEDA appears to increase the efficiency and perhaps theavailability of hydride for a catalyst formed from 2 moles of DMEAH and3 moles of n-butyllithium. In contrast to Examples 33 and 34, thecatalyst system of Examples 35 and 36 has surprisingly completelydifferent behavior. Accordingly Examples 35 and 36 utilized a catalysthaving the empirical formula [DMEA⁻]LiH (Example 35 w/o TMEDA andExample 36 w/ TMEDA 0.5 mole TMEDA per mole total lithium). As isindicated in Table VIII, the % Efficiency of Example 35 and 36 were 35%and 26% respectively. Again assuming little to no participation ofethylbenzene as a chain transfer agent, this would indicate formation ofcatalysts having compositions with empirical or actual chemical formulaeof [DMEA⁻]₃Li₆H₃ and [DMEA⁻]₄Li₈H₄.4TMEDA respectively, where in bothcases only one hydride is available to add to styrene and form thepolymer initiating species. It should be clear from the % Efficiency ofthe catalyst of Examples 33-36, ca. 50%, ca. 66.7%, ca. 33.3% and ca.0.25% that the LOXLiH catalyst and by extension the LOXSH catalyst ofthis invention likely exist as relatively simple aggregates of definedstoichiometry depending upon the reagents used in their formation.Example 37 however might suggest the formation of much more complex yetwell-defined super aggregates can be formed. Thus Example 37 whichutilized a catalyst having the empirical formula [DMEA⁻]Li₃H₂ in a LiH:styrene ratio of 1:18.6 (M_(n) calc=1933) provided a saline hydrideinitiated polystyrene composition with M_(n)=17,972 with a % Efficiencyof ≈11%. This would indicate that only one in nine LiH's were availableto add to styrene and thus initiate polymerization. This might indicatea mixture of aggregates having the empirical formulae [DMEA⁻]₈Li₁₆H₈ and[DMEA⁻]₆Li₁₈H₁₂ in a ratio of 75:25 where one in eight and one in 12LiH's were available to initiate polymerization. Thus, though we wishnot to be bound by such theory as just presented regarding actualchemical formula of the LOXLiH catalyst, Examples 33-37 clearlydemonstrate the four points (1)-(4) above. Example 37 is presented to berepresentative of Examples 33-37.

Example 37 Representative of LOXLiH [DMEA⁻]Li₃H₂.2TMEDA Catalyst UnderHydrocarbon Atmosphere at 82° C.

Anhydrous cyclohexane, 450 ml of 650 ml (506.4 g) was charged to thereactor at 10° C. under a dry hydrogen (11 PSIG H₂) atmosphere. To thestirred solvent (800 RPM, three pitched blade turbines withConfiguration III above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 3.02 g(0.0339 mol.) N,N-dimethylaminoethanol and 7.90 g (0.068 mol) of TMEDAdissolved in 50 ml of the total amount of anhydrous cyclohexane above.The charge vessel and transfer line to the reactor was flushed with a 50ml portion of anhydrous cyclohexane from the total amount above. Next,50.90 ml (0.1018 mole) 2.0 M n-butyllithium in cyclohexane dissolved in65 g (0.61 mole) was transferred through the charge vessel to thereactor over 15 minutes followed by two 50 ml aliquots of the anhydrouscyclohexane from the total amount above. During the organolithium chargeagitation speed was increased to 1130 RPM and the reactor pressuredecreased to 5 PSIG and the temperature increased to 13° C. The reactorhead space was then pressured to 50 PSIG with dry H₂ (through asubsurface feedline) and then vented to 0 PSIG, repeating for a total ofthree times (slowly venting to keep the contents from foaming out of thereactor) leaving the reactor at 46 PSIG. The reactor was then heated to70° C. over 50 minutes with the heating process conducted with 85° C.oil flowing through the reactor jacket. Upon reaching 73° C. and 57 PSIGthe hydrogen atmosphere was vented to a mineral oil bubbler (0 PSIG).Heating was continued until the reactor temperature reached 82° C. andthe vent line began to warm from the condensing cyclohexane vapors thuspurging remaining hydrogen and establishing a hydrocarbon atmosphere.The valve to the mineral oil bubbler was closed and the agitation wasreduced to 794 RPM and styrene monomer feed was initiated, feeding 131.3g (1.26 mol.) of styrene. The styrene was fed through a subsurface feedline (0.02″ ID tip, 1.29 ft/s) against the hydrocarbon atmosphere over aperiod of 30 minutes controlling the reaction temperature at 82° C.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous ethylbenzene. The reactor was pressured to 65 PSIG H₂ withthe pressure dropping to 60 PSIG upon increasing the agitation to 1130RPM. The thus hydrogen quenched anionic polymerization reaction mixturewas transferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water. During the transfer of the unquenched hydridereaction mixture a 10 ml sample of the reaction mixture was obtained.The sample was faintly pink in color and transparent to light with nosettled or suspended solids. Shaking the sample with the air entrappedin the sample vial quenched the faint pink color. The sample wasquenched by the addition of a drop of methanol from a transfer pipet.The methanol quench immediately resulted in the formation and evolutionof hydrogen gas.

The standard work-up and solvent strip from above except that thedistillation was deemed complete when no more ethylbenzene could betaken over head with a nitrogen sparge of the headspace. The resultingresin (154 g) was transferred through the bottom drain valve to apreviously weighed metal tray lined with aluminum foil. The resin wasthen further stripped of ethylbenzene in a vacuum oven which wasgradually heated from 100° C. to 165° C. with the vacuum graduallyincreased from 50.0 mmHg to 1.0 mmHg vacuum. Upon cooling the resultingbrittle colorless resin (128 g) was sampled and analyzed by GPC: M_(n):17,972, M_(w): 37,183, M_(z): 49,015, PD: 1.318, σ_(n)=18,581,_(n)α₃=1.299.

Examples 38-40

Examples 38-40 are examples of hydrogen mediated saline hydrideinitiated polymerization processes involving styrene monomer and otherforms of saline hydride as catalyst. The super active saline hydride(SASH) catalyst of Example 38 was prepared from butyllithium and t-butylalcohol in the presence of TMEDA. This catalyst is sparingly soluble atbest and consequently produced HMSHIP distributions high in molecularweight. The SASH catalyst of Example 39 was prepared from potassiumt-butoxide in addition to butyllithium in the presence of TMEDA. Thiscatalyst was highly effective in forming low molecular weight HMSHIPdistributions however this SASH catalyst process formed undesiredquaternary “tail to head to tail” linkages in the polymer microstructure(Like all other potassium based anionic chain transfer polymerizationreactions). Example 40 utilized a highly active saline hydride (HASH)catalyst formed by feeding styrene monomer to sodium potassium alloydispersion in THF under a hydrogen atmosphere. The HASH catalyst wasrelatively inefficient based on the gram-atoms of sodium and potassiumrequired to produce the obtained molecular weight distribution.Furthermore the HASH catalyst not surprisingly provided a complexmélange of polymer distributions of different microstructures especiallyfragmentation oligomers.

Example 38 Super Active Lithium Hydride Catalyst Process Producing HighMolecular Weight Polystyrene Distribution Composition

Anhydrous ethylbenzene 300 g, was charged to the reactor at 20° C. undera hydrogen atmosphere (0 PSIG). To the stirred solvent (800 RPM, twinpitch blade impellers, blade placement Configuration III) was chargedthrough the charge vessel a solution previously formed from 3.62 g(0.0489 mol.) of tert-butyl alcohol, 69.9 g (0.66 mol.) of ethylbenzene,and 23.50 g (0.202 mol.) of TMEDA. The charge vessel and transfer lineto the reactor was flushed with a 50 g portion of ethylbenzene.Agitation was increased to 1130 RPM and then 54.10 ml (0.11 mole) of 2.0M n-butyllithium dissolved in 100 g of ethylbenzene was transferredslowly through the charge vessel to the reactor. The reactor temperaturerose 5° C. to 25° C. and the pressure increased to 2 PSIG then droppedto −4 PSIG drawing the butyllithium solution and a subsequent 50 g rinsealiquot of ethylbenzene into the reactor. The reactor containing a totalof 570 g (5.4 mol.) of ethylbenzene was heated to 90° C. Trace N₂introduced during the catalyst component charge was purged by pressuringto 50 PSIG with dry H₂ (through the headspace) and venting three times(slowly venting to keep the contents from foaming out of the reactor).The H₂ regulator was set initially to 21 PSIG. Styrene, 462.2 g (4.44mol.), was fed through a subsurface feed line (0.02″ ID tip, 1.2 ft/s)against the hydrogen head pressure over a period of 116 minutescontrolling the temperature at 90° C. and gradually increasing thehydrogen pressure to 41 PSIG. At the end of the styrene feed, themonomer feed line to the reactor, including the alumina columns, wereflushed with 50 ml of anhydrous cyclohexane. The styrene feed and flushto the reactor was deemed complete when no further heat of reaction wasobserved generally signified by the permanent closing of the automatedcontrol valve on the coiling coils. During the course of the run thevalve to the hydrogen regulator was periodically closed to verify uptakeof hydrogen during the styrene feed. The reaction did take up hydrogenalbeit very slowly.

The unquenched content of the reaction mixture was transferred to thewash vessel (N2 atmosphere) previously charged with 300 ml ofdeoxygenated water heated to 65° C. and then washed with deoxygenatedwater (3×300 ml). This reaction mixture was then properly discarded uponseparation of the aqueous quench. During the course of the transfer ofthe unquenched reaction mixture, a 10 ml aliquot of the unquenchedreaction mixture was obtained. This colorless sample was full ofuniformly suspended extremely finely divided solids. The sample wasquenched with methanol resulting in the immediate production andevolution of hydrogen gas from the viscous mixture. GPC analyses of thesample using standard higher molecular weight columns and polystyrenestandards was as follows: GPC MWD of M_(n): 1030, M_(w): 5635, M_(z):10,066 PD: 5.47, σ_(n)=2178, _(n)α₃=4.13.

Example 39 Representative of 80% Monomer Feed Volume for SASH CatalystRuns in Ethylbenzene at Moderate Temperatures 70° C. w/ OligomerMicrostructure Analysis

Anhydrous ethylbenzene 200 g of 300 g (2.83 mole), was charged to thereactor at 20° C. under a dry nitrogen atmosphere. To the stirredsolvent (800 RPM, twin pitch blade impellers, blade placementConfiguration I) was charged through the charge vessel a solutionpreviously formed from 4.57 g (0.0407 mol.) potassium t-butoxide, 44 g(0.41 mol.) ethylbenzene and 20.83 g (0.179 mol.) TMEDA. The chargevessel and transfer line to the reactor was flushed with a 50 g portionof ethylbenzene of the 300 g above. Next 20.34 ml (0.0407 mole) 2.0 Mn-butyllithium was transferred through the charge vessel to the reactorfollowed by a 50 g aliquot of ethylbenzene from above. The reactor washeated to 65° C. Agitation was then increased to 1130 RPM and thereactor purged of N₂ by pressuring to 65 PSIG with dry H₂ (through theheadspace) and venting three times (slowly venting to keep the contentsfrom foaming out of the reactor). The H₂ regulator was set to 11 PSIGand 800 g (7.68 mol.) styrene was fed through a subsurface feed line(0.01″ ID tip, 5.2 ft/s) against the hydrogen head pressure over aperiod of 183 minutes controlling the temperature at 70° C. At the endof the styrene feed, the monomer feed line to the reactor, including thealumina columns, were flushed with 50 ml of anhydrous cyclohexane. Thestyrene feed and flush to the reactor was deemed complete when nofurther heat of reaction was observed generally signified by thepermanent closing of the automated control valve on the coiling coils.

The unquenched polymerization reaction mixture was transferred withpositive H₂ pressure to the wash vessel previously heated (N₂atmosphere) and previously charged with 300 ml of deoxygenated wateralong with 500 ml of recovered cyclohexane distilled from previous runs.During the transfer of the unquenched reaction mixture a 10 ml sample ofthe reaction mixture was obtained for analysis. The sample was red incolor and transparent to light giving it an appearance similar to thecolor of a living APS process sample. The sample's appearance wascompletely unlike the characteristic dark black-red (black cherry) colorof samples anionic chain transfer polymerization conducted in theabsence of a hydrogen atmosphere. Such samples of SASH catalyst wherethe catalyst components are combined under N₂ before forming the hydridegenerally can contain large (mm size) catalyst particles. The sample isquenched by the addition of a drop of methanol which immediatelyquenches the red color and results in the immediate formation andevolution of hydrogen gas. GPC Analysis of the crude quenched reactionmixture was as follows: M_(n): 367, M_(w): 497, M_(z): 695, PD: 1.35,σ_(n)=218, _(n)α₃=2.38.

The standard work-up and strip procedure from above provided 1303 g ofsolution. Wiped film evaporation (WFE, 2″ glass Pope Still, operated at50.0 mmHg vacuum, 140° C., 60% of full wiper speed, feeding at 1.0liters/hr) produced 827.9 g of a SASH PS distribution having GPC MWD ofM_(n): 376, M_(w): 508, M_(z): 707, PD: 1.35, σ_(n)=223, _(n)α₃=3.34. Asecond WFE operation (0.1-0.3 mmHg vacuum, 172.5° C., 60% of full wiperspeed, feeding at 1.0 liters/hr) provided 608.7 of a SASH PSdistribution having 0.99 GPC area % styrene dimer content and a GPC MWDof M_(n): 486, M_(w): 593, M_(z): 750, PD: 1.22, σ_(n)=228, _(n)α₃=2.15.A third WFE operation was performed to obtain the low molecular weightoligomers in order to determine the SASH PS distribution microstructure.Thus a 180.2 g sample of the 608.7 g product distribution recovered fromthe 2^(nd) WFE operation was stripped of oligomers 0.1 mmHg vacuum,199.5° C., wiper speed 85% of full rate, feeding at 2.0 g/min.). Thisthird WFE operation produced 33.17 g of a styrene oligomer mixturehaving GPC MWD: of M_(n): 332, M_(w): 348, M_(z): 363, PD: 1.048. GCanalysis indicated that 93.49% of the chains had the desired “head totail” microstructure, with only a 0.11% of the chains having thefragmented (FW_(i)−14) microstructure (See FIG. 7). The gas chromatogramin FIG. 7 demonstrates the oligomer microstructure purity: 93.49% “Headto Tail” Microstructure; 6.4% of oligomers w/ one quaternary “tail tohead to tail” linkage; and 0.11% fragmentation oligomers

Example 40 Highly Active Saline Hydride Catalyst Hydrogen MediatedStyrene Polymerization w/ Oligomer Microstructure Analysis

The anionic chain transfer process was conducted in the modified 2-literautoclave reactor described in U.S. Pat. Nos. 5,777,162 and 5,866,720.Anhydrous tetrahydrofuran 818 g and 6.2 g (0.183 g-atoms alkali metal)of sodium potassium alloy (NaK₂) were charged to the reactor at 20° C.under a dry nitrogen atmosphere. The unstirred reaction mixture waspurged of nitrogen with hydrogen (3×70 PSIG) and the pressurized to 70PSIG H₂. High speed high sheer mixing (1900 RPM) applied and styrene,208.0 g (2.00 mole), was fed over 73 minutes (3.15 ml/min) to thereaction mixture. During the styrene monomer feed the reactor pressurewas maintained between 70 and 60 PSIG H₂. Upon completion of the feedthe reactor was vented of H₂ and the reaction mixture was carefullyquenched with isopropyl alcohol. A sample of the quenched reactionmixture was analyzed by GPC and had the following MWD: M_(n): 591,M_(w): 943, M_(z): 1438, PD: 1.60, σ_(n)=456, _(n)α₃=2.38. The reactionmass is transferred to a creased wash reactor containing ethylbenzenewater washed and stripped of THE. Further stripping on a wiped filmevaporator WFE (2″ glass Pope Still, graphite blades, operated at 300.0mmHg vacuum, 140° C., 60% of full wiper speed feeding at 1.0 liter/hrrate) produced 191 g of a polystyrene resin having GPC MWD: M_(n): 603,M_(w): 956, M_(z): 1373, PD: 1.58, σ_(n)=461, _(n)α₃=1.906. A 164 gsample of the 191 g from above was subjected to a second WFE operation(at 0.4 mmHg vacuum, 230° C., 60% of full wiper speed feeding at 1.0liter/hr rate) yielding 153.6 g of a resin having GPC MWD: M_(n): 802,M_(w): 1081, M_(z): 1418, PD: 1.35, σ_(n)=473, _(n)α₃=1.645. The secondWFE operation provided 18.2 g of complex mixture of dimers, trimers,tetramers, pentamers and hexamers. GC analysis demonstrates that thiscomplex mixture arises from reaction pathways that include head to tailpolymerization, chain isomerization and chain fragmentationpolymerization (see FIG. 5). Gas chromatogram shown in FIG. 5 includesdemonstrates this complex mixture of microstructures which includes thedesired “head to tail” linkages as well as undesired quaternary carbonlinkages, fragmentation polymerization (FW_(i)−14) and (FW_(i)+14)oligomers as well as even “tail to tail” styrene oligomers arising fromradical coupling reactions.

Upon completion of preparation of the dimer stripped LOXLiH and LOXMgH₂hydrogen mediated saline hydride initiate polymerization productdistributions. Eleven of these compositions were brominated according tothe process technology of PCT Pub. No.: WO2010/127091 (U.S. Pat. No.8,802,787 B2) to form brominated anionic chain transfer vinylaromaticpolymers (Br-ACTVAP). The average and standard deviation of the physicalproperties of these brominated polymers are listed below as well as theproperties of the Br-ACTVAP formed by combining and then stripping theproduct distribution of Examples 14-15, that dimer stripped compositionhaving M_(w)=731 and PD_(n)=1.38. The compositions were further testedas polymeric flame retardants in high impact polystyrene (HIPS) and werefound to provide flame retarded (UL 94 VO at ⅛″ and 1/16″) HIPSformulations with excellent overall properties including color (YI),Izod Impact, heat distortion temperature and VICAT softeningtemperature.

Br-ACTVAP Example Average Standard Property 14 + 15 All Dev. % Br (NMR)73.0 73.7 0.3 T_(g) (° C.) 112.5 118.9 4.2 Thermally Labile Bromine 7590.5 19.6 (ppm) at 300° C. 15 minutes Color Solution L 99.5 99.2 0.2 a−1.39 −1.8 0.3 b 3.68 5.1 1.0 Delta E 3.97 5.5 1.0 COLOR Solids L 96.4195.0 2.3 a −0.64 −0.8 0.1 b 2.94 3.6 0.4 Yellowness Index 4.97 6.2 0.6Thermal Color 10.03 13.8 1.8 (250° C. 15 min.) Delta E TGA underNitrogen  1% Wt. Loss (° C.) 314.90 313.7 13.7  5% Wt. Loss (° C.)356.56 356.7 10.2 10% Wt. Loss (° C.) 370.82 370.7 7.7 50% Wt. Loss (°C.) 407.94 404.7 5.6 90% Wt. Loss (° C.) 437.11 454.1 14.6 GPC (UVDetector) M_(n) 1996 1949.7 119.0 M_(w) 2565 2519.4 196.2 PD_(n) 1.2851.3 0.0 σ_(n) 1066 1052.5 107.3

In that the catalyst composition of Examples 14 and 15 were comprised of[DMEA⁻]Li₃H₂.1.0 TMEDA, and this composition provided excellent over allproperties once brominated, further development of this particularLOXLiH catalyst and the resulting hydrogen mediated anionic polystyrene(HMAPS) was deemed warranted.

Examples 41-42

Examples 41-42 further demonstrate experiments designed to furtherelucidate the complex stoichiometry of the [DMEA⁻]_(x)Li_(y)H_(z). TheseExamples were run under identical conditions except for the charge ratioof the DMEAH:n-butyllithium. The numerical details of these two Examplesare presented in Table IX. The experimental details are presented below.

Example 41 Representative of [DMEA⁻]Li₃H₂ Catalyst Under HydrocarbonAtmosphere at 77-79° C.

Anhydrous cyclohexane, 220 ml of a total of 500 ml (385.3 g) was chargedto the reactor at 37.6° C. under a dry hydrogen (20 PSIG H₂) atmosphere.To the stirred solvent (600 RPM, four pitched blade turbines withConfiguration IV above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 5.18 g(0.0581 mol.) N,N-dimethylaminoethanol dissolved in 20 ml of the totalamount of anhydrous cyclohexane above. The charge vessel and transferline to the reactor was flushed with a 50 ml portion of anhydrouscyclohexane from the total amount above. Next, 44.95 ml (0.0899 mole)2.0 M n-butyllithium in cyclohexane dissolved in 120 ml cyclohexane ofthe 500 ml total above was transferred through the charge vessel to thereactor over 20 minutes followed by a 50 ml aliquot of the anhydrouscyclohexane from the total amount above. During the organolithium chargeagitation speed was maintained at 600 RPM and the reactor pressuredecreased to 18 PSIG after having raised to 24 PSIG and the temperatureincreased to 39.9° C. The reactor head space was then pressured to 53PSIG with dry H₂ (through a subsurface feedline), agitation wasincreased to 1000 RPMs and the catalyst solution heated over a period of30 minutes to 69.9° C. During the course of the heating process the H₂pressure reached 64 PSIG. The reactor was further pressured to 76 PSIGand left to stir for 2.5 hours before venting to 0 PSIG at 73.2° C. Thereactor was then heated to 92° C. over 30 minutes with the heatingprocess conducted with 115° C. oil flowing through the reactor jacket.Upon reaching 92° C. and 8 PSIG the hydrogen atmosphere was vented to amineral oil bubbler to 4 PSIG when cyclohexane vapors began to condensein the overhead establishing a hydrocarbon atmosphere. The valve to themineral oil bubbler was closed and the agitation was reduced increasedto 1100 RPM and the reactor was cooled to 76.9° C. and −2 PSIG pressure.

Styrene monomer 98.0 g (0.94 mol.) was combined with 90 g ofcyclohexane. The styrene/cyclohexane feed was fed through a subsurfacefeed line (0.02″ ID tip) against the hydrocarbon atmosphere over aperiod of 60 minutes (5.0 ml/min.) controlling the reaction temperatureat the reaction temperature never rising above 79.4° C. (80-85° C.) oilon the jacket.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous cyclohexane. The reactor was pressured to 65 PSIG H₂. Thehydrogen quenched anionic polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml ofdeoxygenated water. During the transfer of the unquenched hydridereaction mixture a 10 ml sample of the reaction mixture was obtained.The sample was faintly pink in color and transparent to light with nosettled or suspended solids. Shaking the sample with the air entrappedin the sample vial quenched the faint pink color. The standard work-upand solvent strip from above except that the distillation was deemedcomplete when no more ethylbenzene could be taken over head with anitrogen sparge of the headspace. The resulting resin (90 g) wastransferred through the bottom drain valve (with great difficulty andthe aid of a high temperature air gun) to a previously weighed metaltray lined with aluminum foil. Analysis of the cooled resin by GPCprovided the following: M_(n): 13,845, M_(w): 38,933, M_(z): 65,777, PD:2.812, σ_(n)=18,637, _(n)α₃=2.84.

Examples 42-51

Examples 42 through 51 demonstrate the improved yield generally broughton by reduced formation of the co-product ethylbenzene and styrene dimer(increased M_(n)) resulting from faster relative feed rates and slightlyreduced hydrogen pressure when using TMEDA as a promotor at a catalystconcentration that varies over the course of the feed from about 275±50ppm LiH down to about 80±20 ppm LiH. The detail and results for theseExamples is presented in Table X. In the course of running this set ofExamples it was found that the presence of TMEDA during catalystformation can have a deactivating affect. Thus for Example 42-47 TMEDAwas charged to the reactor only after combining the DMEAH andn-butyllithium under a hydrogen atmosphere wherein the reactor wouldhave contained some amount of a heal from the previous run (except forExample 42 where the reactor had be previously cleaned). Thus forExamples 42-47 M_(n) generally increases with increased feed rate anddecreased H₂ pressure. Example 48 however, M_(n) dropped to 457 Daltonswith the increased feed rate and decreased H₂ (9 PSIG) pressureemployed. A period of time greater than 2 weeks had past been runningExample 47 and 48 and thus during this time any reaction mixture—whichwould contain TMEDA—left on the surfaces of the reactor had flowed tothe bottom of the reactor. Additionally because the reactor had beenleft for such an extended period a 500 ml flush of anhydrous cyclohexanewas used to purge any remnant of Example 47 before forming the catalystfor Example 48. Thus on Example 49 TMEDA was charged to the reactorbefore charging n-butyllithium and as a consequence this Exampleproduced a HMAPS distribution having an M_(n)=540 despite using anincreased H₂ (11 PSIG) pressure. Thus on the subsequent two runsExamples 50 and 51, the catalyst component charges were made to a wellrinsed reactor. It is surmised that TMEDA promotes the formation ofsuper active yet insoluble lithium hydride which would be formeddirectly from n-butyllithium, TMEDA and hydrogen without theintermediary DMEAH which provides the hydrocarbon soluble form of LiH.Thus Examples 50 and 51 together is representative of the Examples ofTable X and are deemed as representative of the preferred process of theExamples of that Table.

Examples 50 and 51 Representative of Full Scale Monomer Feed Volume for[DMEA⁻]₄Li₆H₂.2TMEDA Catalyst at 80° C.

Anhydrous cyclohexane, 150 ml of 300 ml (233.7 g) was charged to thewell rinsed reactor at 37° C. under a dry hydrogen (16 PSIG H₂)atmosphere. To the stirred solvent (800 RPM, four pitched blade turbineswith Configuration IV above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 2.53 g(0.0284 mol.) N,N-dimethylethanolamine, 20 g of a total of 170.0 g (1.60mol) ethylbenzene and 50 ml of the 300 ml above. Next, 21.25 ml (0.0425mole) 2.0 M n-butyllithium dissolved in 120 g anhydrous ethylbenzene(from the 170 g above) and another 50 ml aliquots of the anhydrouscyclohexane from the total amount above were combined in the chargevessel and then pressure transferred over a period of 15 minutes to thestirred (800 RPM) reaction mixture under hydrogen. At the end of theorganolithium charge agitation speed was increased to 1130 RPM and thereactor pressure decreased from a peak pressure of 19 PSIG to an endingpressure of 14 PSIG. During the course of the catalyst formation thetemperature increased 2-3° C. Finally, 3.40 g (0.0293 mol) of TMEDAdissolved in 30 g anhydrous ethylbenzene was combined with with the last50 ml aliquot of anhydrous cyclohexane and pressure transferred to thestirred reaction mixture. The reactor head space was vented to 0 PSIGand then pressured to 45 PSIG with dry H₂ (through a subsurfacefeedline). The reactor was then heated to 73.2° C. with the pressuringbuilding to 63 PSIG. The heating was conducted with 80° C. oil flowingthrough the reactor jacket. Upon reaching a reaction temperature of 73°C. the styrene monomer feed was initiated, feeding 1058.7 g (10.17 mol.)of styrene. The styrene was fed through a subsurface feed line (0.02″ IDtip) against the hydrogen head pressure of 11 PSIG over a period of 116minutes attempting to control the reaction temperature at 80° C. Within10 minutes of initiation of the monomer feed the reactor temperaturereached 82.8° C. Periodically the hydrogen uptake was monitored byclosing the valve to the regulator and timing the period required todrop 5 PSIG. Thus the period in seconds required for the pressure todrop (−1) one PSIG was recorded. When this value was adjusted forestimated reactor headspace, the hydrogen uptake in terms of mole H₂ permole of styrene feed appeared constant or near constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous cyclohexane. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml of 5 wt %aqueous H₂SO₄. Thus the reaction mixture was quenched with care in thewash reactor. The charge vessel and the reactor were then rinsed with300 ml of anhydrous cyclohexane and the rinse solution transferred tothe wash reactor and combined with the crude quenched reaction mixture.

The above process was repeated as Example 51 with the identical chargesand conditions to within minor run to run variations in measuring outthe reagents and reproducing the conditions except that 10 PSIG H₂ wasemployed. Despite the near 10% reduction in H₂ activity, hydrogen uptakewas still faster for Example 51 vs. Example 50.

During the transfer of the unquenched reaction mixtures (Examples 50 and51) 10 ml samples of the individual reaction mixtures were obtained foranalyses. The samples were slightly pink to water white—i.e. essentiallycolorless and transparent to light—with no settled or suspended solids.Any color was quenched by gently shaking/swirling or otherwisecontacting the mixtures with air. The samples were submitted for GPCanalysis without quenching the crude reaction mixtures. The GPC analysisexcluding ethylbenzene but including the dimer content was as follows:Example 50 M_(n): 525, M_(w): 804, M_(z): 1165, PD: 1.449, σ_(n)=383,_(n)α₃=2.075 and M_(w) 10% High=2048; Example 51 M_(n): 506, M_(w): 758,M_(z): 1080, PD: 1.425, σ_(n)=357, _(n)α₃=2.001; and M_(w) 10%High=1844.

The standard work-up from above provided 2613 g of solution. Wiped filmevaporation (WFE, 2″ glass Pope Still, operated at 50.0 mmHg vacuum,140° C., wiper speed 60% of full rate, feeding at 1.0 liters/hr)produced 1997.5 g HMAPS distribution having GPC MWD including dimer ofM_(n): 519, M_(w): 783, M_(z): 1122, PD: 1.452, σ_(n)=370,_(n)α₃=2.0274: and M_(w) 10% High=1922. A second WFE operation (0.1-0.3mmHg vacuum, 172.5° C., wiper speed 60% of full rate, feeding at 1.0liters/hr) provided 1800.0 g of a HMAPS distribution having 2.38 GPCarea % styrene dimer content and a GPC MWD of M_(n): 601, M_(w): 836,M_(z): 1142, PD: 1.391, σ_(n)=326, _(n)α₃=1.923; and M_(w) 10%High=1955.

Examples 52-59

Examples 52 through 59 demonstrate the HMAPS process can be run withoutthe benefit of an added aromatic solvent including ethylbenzene. TheseExamples well demonstrate that the HMAPS process is very robust in thatit reproducibly produces near identical HMAPS distributions under avariety of process conditions. Examples 56-59 demonstrate that anyprocess benefit provided by the use of the promoter TMEDA, can be offsetwith increased hydrogen pressure thereby reducing and even eliminatingthe use of a promotor. This set of high yield Examples (polymer yieldfrom about 96 to about 97% yield; and a yield of dimer stripped polymerfrom about 86% to about 87%) produced HMAPS distributions with asymmetryvalues in the range of about 1.67 to 2.00 and dimer stripped HMAPPSdistributions with asymmetry values in the range of about 1.63 to 1.82.Examples 58 and 59 are deemed representative of the Examples inconducting these two Examples it was inadvertently discovered thatcatalyst aging provided a more active and preferred catalyst.

Examples 58 and 59 Representative of Full Scale Monomer Feed Volume for[DMEA⁻]₄Li₆H₂ Catalyst at 80° C.

Anhydrous cyclohexane, 200 ml of 500 ml (389.5 g) was charged to thewell rinsed reactor at 37° C. under a dry hydrogen (16 PSIG H₂)atmosphere. To the stirred solvent (800 RPM, four pitched blade turbineswith Configuration IV above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 2.55 g(0.0285 mol.) N,N-dimethylethanolamine, 70 ml of a total of 500 ml ofcyclohexane of the 500 ml above. Next, 21.47 ml (0.0429 mole) 2.0 Mn-butyllithium further dissolved in 170 ml the anhydrous cyclohexanefrom the 500 ml sbove were transferred to the charge vessel and thenpressure transferred over a period of 15 minutes to the stirred (800RPM) reaction mixture under hydrogen. At the end of the organolithiumcharge agitation speed was increased to 1130 RPM and the reactorpressure decreased from a peak pressure of 19 PSIG to an ending pressurereturning to 16 PSIG. During the course of the catalyst formation thetemperature increased 2-3° C. The reactor head space was vented to 0PSIG and then pressured to 45 PSIG with dry H₂ (through a subsurfacefeedline). The reactor was then heated to 73.2° C. with the pressuringbuilding to 63 PSIG. The heating was conducted with 80° C. oil flowingthrough the reactor jacket. Upon reaching a reaction temperature of 73°C. the styrene monomer feed was initiated, feeding 1061.0 g (10.19 mol.)of styrene. The styrene was fed through a subsurface feed line (0.02″ IDtip) against the hydrogen head pressure of 15-17 PSIG over a period of117 minutes controlling the reaction temperature at 80° C. Within 10minutes of initiation of the monomer feed the reactor temperaturereached 81.7° C. Periodically the hydrogen uptake was monitored byclosing the valve to the regulator and timing the period required todrop 5 PSIG. Thus the period in seconds required for the pressure todrop (−1) one PSIG was recorded. When this value was adjusted forestimated reactor headspace, the hydrogen uptake in terms of mole H₂ permole of styrene feed appeared constant or near constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous cyclohexane. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml of 5 wt %aqueous H₂SO₄ and ≈250 g of ethylbenzene recovered from the wiped filmevaporator from the solvent strip of a previous runs. Thus the reactionmixture was quenched with care in the wash reactor. The charge vesseland the reactor were then rinsed with 200 ml of anhydrous cyclohexaneand the rinse solution transferred to the wash reactor and combined withthe crude quenched reaction mixture.

The above process was repeated as Example 59 with the identical chargesand conditions to within minor run to run variations in measuring outthe reagents with the exception that the catalyst was allowed to age for3 hours consequently the H₂ was adjusted down to 14 PSIG in order tomatch the uptake of Example 58. It is clear however that the HMAPSdistributions produced were near identical except that Example 59 had alower asymmetry than Example 58; asymmetry of 1.826 vs. 1.928respectively.

During the transfer of the unquenched reaction mixtures (Examples 58 and59) 10 ml samples of the individual reaction mixtures were obtained foranalyses. The samples were slightly pink to water white—i.e. essentiallycolorless and transparent to light—with no settled or suspended solids.Any color was quenched by gently shaking/swirling or otherwisecontacting the mixtures with air. The samples were submitted for GPCanalysis without quenching the crude reaction mixtures. The GPC analysisexcluding ethylbenzene but including the dimer content was as follows:Example 58 M_(n): 570, M_(w): 890, M_(z): 1276, PD: 1.434, σ_(n)=427,_(n)α₃=1.928 and M_(w) 10% High=2168; Example 59 M_(n): 584, M_(w): 909,M_(z): 1286, PD: 1.415, σ_(n)=436, _(n)α₃=1.826; and M_(w) 10%High=2166.

The standard work-up from above provided 2487 g of solution. Wiped filmevaporation (WFE, 2″ glass Pope Still, operated at 50.0 mmHg vacuum,140° C., wiper speed 60% of full rate, feeding at 1.0 liters/hr)produced 2094.3 g (2052 g when adjusted for dime content of recycleethylbenzene from the WFE in the wash) HMAPS distribution having GPC MWDexcluding dimer of M_(n): 690, M_(w): 970, M_(z): 1328, PD: 1.406,σ_(n)=440, _(n)α₃=1.889: and M_(w) 10% High=2263. The total distributionincluding dimer formed during the reaction when statistically correctedis estimated as follows: M_(n): 612, M_(w): 919.18, M_(z): 1294, PD:1.406, σ_(n)=434, _(n)α₃=1.8791. A second WFE operation (0.1-0.3 mmHgvacuum, 160° C., wiper speed 65% of full rate, feeding at 1.0 liters/hr)provided 1825.7 g of a HMAPS distribution having 0.48 GPC area % styrenedimer content and a GPC MWD of M_(n): 704, M_(w): 984, M_(z): 1334, PD:1.398, σ_(n)=444, _(n)α₃=1.815; and M_(w) 10% High=2268.

A third WFE operation was performed to obtain the low molecular weightoligomers in order to determine the HMAPS PS distributionmicrostructure. Thus a 125 g sample of the 1825 g product distributionrecovered from the 2^(nd) WFE operation was stripped of oligomers (0.13mmHg vacuum, 199.5° C., wiper speed 85% of full rate, feeding at 2.0g/min.). This third WFE operation produced 22 g of a styrene oligomer GCanalysis of which indicated that 99.97% of the chains had the desired“head to tail” microstructure, with only a trace if any of chains havingassumed to be (FW_(i)−2) microstructure wherein lithium hydrideelimination had occurred producing an unsaturated chain end (See FIG.16). A spiking experiment of authentic (FW_(i)−14) material clearlyproved the composition to be free of this microstructure.

Examples 60-67

Examples 60 through 67 demonstrate the HMAPS process can be run withdried (<10 ppm moisture) recycled solvent obtain from previous Examples.Recycle of solvent entails combining cyclohexane and ethylbenzene fromthe wash reactor strip and the first WFE operation, azeotropicdistillation of water followed by simple distillation to a pottemperature of about 140° C. at one atmosphere. Further drying isaccomplished with the use of activated molecular sieves. Due to the lessthan preferred process conditions employed Examples 61 and 62; and to alesser extent Examples 60 and 67, these Examples produced high molecularweight material at the end of the monomer feed as evidenced by the MWDformed and the reduced uptake of H₂ during the last 8 to 13% of thefeed.

Of the runs Example 61 produced the least preferred result forming ahigh molecular weight tail with M_(w) 10% High of 2629 Daltons. ForExample 61 a lower catalyst loading was employed and thus under theresulting less preferred relative styrene to catalyst feed rate,hydrogen mass transfer became inefficient during the last 13% of thefeed. Example 60 is comparable to Example 58 (no ageing) and 59 (3 hrageing) except that the catalyst was aged for 1 hr and the solventcontained recycle ethylbenzene. Initially the catalyst appeared moreactive than either Example 58 or 59; however catalyst activity appearedto fall off during the last 8 minutes of the styrene feed producing aslightly higher molecular weight. For Example 61 an attempt was made toreduce the catalyst loading by 20% however this resulted in a highmolecular weight tail when during the last 13 minutes of the feedHydrogen uptake slowed. In the course of further establishing the scopeof this invention (Examples 62-67) it was found that a reduction inmixing (1000 rpms vs. the standard 1130 rpms) could be offset by: i)increased temperature; and/or ii) reduced total monomer feed; and/oriii) decreased monomer feed rate; and/or iv) increase hydrogen pressure;v) increased catalyst aging time. The results of these experiments arepresented in Table XII. Examples 64 and 65 are deemed representative.

Examples 64 and 65 Representative of Full Scale Monomer Feed Volume for[DMEA⁻]₄Li₆H₂ Catalyst at 90° C. with Recycle Solvent Recovered fromPrevious Examples

Recycled anhydrous solvent [79.4 wt % cyclohexane (CH), 20.6 wt %Ethylbenzene (EB)], 220 ml of 320 ml (252.65 g) total was charged to thewell rinsed reactor at 37° C. under a dry hydrogen (16 PSIG H₂)atmosphere. To the stirred solvent (800 RPM, four pitched blade turbineswith Configuration IV above) was charged through the charge vessel viapositive nitrogen pressure, a solution previously formed from 2.55 g(0.0285 mol.) N,N-dimethylethanolamine and 20 ml of cyclohexane furthercombined with 50 ml of the recycle solvent from above. Next, 21.47 ml(0.0429 mole) 2.0 M n-butyllithium dissolved in 120 ml the anhydrouscyclohexane was transferred to the charge vessel and further combinedwith 50 ml of the recycle solvent (with little if any back mixing) fromabove. This unmixed solution was then pressure transferred over a periodof 15 minutes to the stirred (800 RPM) reaction mixture under hydrogen.At the end of the organolithium charge agitation speed was increased to1130 RPM and the reactor pressure decreased from a peak pressure of 19PSIG to an ending pressure returning to 16 PSIG. During the course ofthe catalyst formation the temperature increased 2-3° C. The reactorhead space was vented to 0 PSIG and then pressured to 45 PSIG with dryH₂ (through a subsurface feedline). The reactor was then heated to 72°C. with the pressuring building to 63 PSIG and further pressured to 72PSIG. The heating was conducted with 80° C. oil flowing through thereactor jacket—holding the reactor at 72° C. and 72 PSIG for 60 minutesbefore venting to 17 PSIG. The reactor was then heated to 82° C. withthe pressuring maintained at 17 PSIG by venting as needed. The heatingwas conducted with 90° C. oil flowing through the reactor jacket—holdingthe reactor at 82° C. and 17 PSIG for 75 minutes at which time styrenemonomer feed was initiated, feeding 1015.0 g (9.75 mol.) of styrene. Thestyrene was fed through a subsurface feed line (0.02″ ID tip) againstthe hydrogen head pressure of 13-15 PSIG over a period of 119 minutescontrolling the reaction temperature at 80° C. Within 10 minutes ofinitiation of the monomer feed the reactor temperature reached 81.7° C.Periodically the hydrogen uptake was monitored by closing the valve tothe regulator and timing the period required to drop 5 PSIG. Thus theperiod in seconds required for the pressure to drop (−1) one PSIG wasrecorded. When this value was adjusted for estimated reactor headspace,the hydrogen uptake in terms of mole H₂ per mole of styrene feedappeared constant or near constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous cyclohexane. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml of 5.13 g ofAcetic Acid dissolved in 300 g H₂O and 300 recovered solvent previouslyrecovered from the initial solvent strip of a previous runs. Thus thereaction mixture was quenched with care in the wash reactor. The chargevessel and the reactor were then rinsed with 200 ml of recycle solventand the rinse solution transferred to the wash reactor and combined withthe crude quenched reaction mixture.

The above process was repeated as Example 65 with the identical chargesand conditions to within minor run to run variations in measuring outthe reagents with the exception that 1035.8 g of styrene was fed oer121minutes the catalyst was allowed to age for 34 minutes at 72° C. and 26minutes at 82° C. It is clear that the HMAPS distributions produced werenear identical to within the experimental error of the GPC analyses.

During the transfer of the unquenched reaction mixtures (Examples 64 and65) 10 ml samples of the individual reaction mixtures were obtained foranalyses. The samples were slightly pink to water white—i.e. essentiallycolorless and transparent to light—with no settled or suspended solids.Any color was quenched by gently shaking/swirling or otherwisecontacting the mixtures with air. The samples were submitted for GPCanalysis without quenching the crude reaction mixtures. The GPC analysisexcluding ethylbenzene but including the dimer content was as follows:Example 64 M_(n): 550, M_(w): 835, M_(z): 1173, PD: 1.405, σ_(n)=396,_(n)α₃=1.832 and M_(w) 10% High=1982; Example 65 M_(n): 558, M_(w): 848,M_(z): 1188, PD: 1.401, σ_(n)=402, _(n)α₃=1.805; and M_(w) 10%High=2003.

The standard work-up from above provided 2487 g of solution. Wiped filmevaporation (WFE, 2″ glass Pope Still, operated at 50.0 mmHg vacuum,140° C., wiper speed 60% of full rate, feeding at 1.0 liters/hr)produced 1947 g HMAPS distribution having GPC MWD including dimer ofM_(n): 562, M_(w): 848, M_(z): 1186, PD: 1.509, σ_(n)=401, _(n)α₃=1.811:and M_(w) 10% High=2002. A second WFE operation (0.1-0.3 mmHg vacuum,160° C., wiper speed 65% of full rate, feeding at 1.0 liters/hr)provided 1716 g of a HMAPS distribution having 0.13 GPC area % styrenedimer content and a GPC MWD of M_(n): 695, M_(w): 935, M_(z): 12284, PD:1.345, σ_(n)=408, _(n)α₃=1.681; and M_(w) 10% High=2064.

A third WFE operation was performed to obtain the low molecular weightoligomers in order to determine the HMAPS PS distributionmicrostructure. Thus a 125 g sample of the 1825 g product distributionrecovered from the 2^(nd) WFE operation was stripped of oligomers (0.13mmHg vacuum, 199.5° C., wiper speed 85% of full rate, feeding at 2.0g/min.). This third WFE operation produced 22 g of a styrene oligomer GCanalysis of which indicated that 99.93% of the chains had the desired“head to tail” microstructure, with only a trace if any of chains havingassumed to be (FW_(i)-2) microstructure wherein lithium hydrideelimination had occurred producing an unsaturated chain end (See FIG.17).

Examples 68-74

Examples 68 through 74 demonstrate the HMAPS process can be run with100% dried (<10 ppm moisture) recycled solvent obtain from previousExamples. As above recycle of solvent entails combining cyclohexane andethylbenzene from the wash reactor strip and the first WFE operation,azeotropic distillation of water followed by simple distillation to apot temperature of about 140° C. at one atmosphere. Further drying isaccomplished with the use of activated molecular sieves. Like above, dueto the less than preferred process conditions employed—mixing of <1000RPMs for the reactor geometry employed—Examples 68 and 72; and to alesser extent Examples 67 and 70 produced high molecular weight materialat the end of the monomer feed as evidenced by the MWD formed and thereduced uptake of H₂ during the last 8 to 13% of the feed. It isimportant to note that Examples 68 and 69 are near identical to Examples66 and 67 from above except for the change in the solvent used tofurther dilute the 2.0 M n-butyllithium before charging. In Example 66and in Example 67, fresh anhydrous cyclohexane was used to initiallydissolve the organolithium reagent. Whereas in Examples 68 and 69recycle solvent comprised of 93% cyclohexane and 7% ethylbenzene wasemployed. This charge protocol surprisingly formed a much more activecatalyst as evidenced by the slightly lower molecular weightdistribution (M_(n)=550 and M_(n)=558 [Ex. 64 and 65 respectively] vs.M_(n)=532 and M_(n)=533 [Ex. 68 and 69 respectively]) at even lowerhydrogen pressure (17 to 19 PSIG vs. 13 to 14 PSIG respectively).Examples 70-73 demonstrate that the activity of the catalyst formed byfirst dilution with some amount of ethylbenzene (without any promoterused in the process) could be curtailed by reducing the RPMs of theagitator and hence amount of mixing during the polymerization. Howeverthis was less preferred in that there was a propensity to form highmolecular material at the end of the styrene feed which could be offsetby increasing the RPMs and/or the hydrogen pressure and/or reducing thetotal amount of styrene monomer fed.

Examples 72 and 73 demonstrate that having more ethylbenzene present hadless of an affect than forming the catalyst at a slightly reduce RPMs.Accordingly the catalyst is generally formed at 800 RPM which issufficient for effective mass transfer of hydrogen to the condensedphase during catalyst formation with the present reactor geometry. ForExample 73 the catalyst components were combined at 500 RPMs mixingwhich is less sufficient than 800 but clearly adequate to formsurprisingly an even more active catalyst. In Example 74200 RPMs and 2PSIG hydrogen was used to form the catalyst. This catalyst was initiallyvery active and had to be run at 9 to 11 PSIG and even at that hydrogenactivity H₂ uptake was too great. Surprisingly this catalyst althoughvery active at the start became less and less active producing a veryasymmetric distribution high in the lower molecular weight chains andhaving a M_(w) 10% High of 3323 Daltons. Thus it is desirable to reducethe complex formed from [DMEA⁻]Li and n-butyllithium as it is formedwhen forming the catalyst at temperatures well above cryogenicconditions. Though we wish not to be bound by theory it is thought thatcontrolling the rate of the reduction by controlling mixing and hydrogenmass transfer helps precondition the catalyst to form the most activeform of catalyst aggregates in the hydrocarbon solution. Thus Examples72 and 73 are deemed representative of this set (68 through 74) ofExamples and described in greater detail below.

Examples 72 and 73 Representative of Full and 90% Scale Monomer FeedVolume for [DMEA⁻]₄Li₆H₂ Catalyst at 90° C. with 100% Recycle SolventRecovered from Previous Examples

Recycled anhydrous solvent [85.0 wt % cyclohexane (CH), 15.0 wt %Ethylbenzene (EB)], 220 ml of 500 ml (392 g) total was charged to thewell rinsed reactor at 37° C. under a dry hydrogen (16 PSIG H₂)atmosphere. To the stirred solvent (800 RPM, four pitched blade turbineswith Configuration IV above) was charged through the charge vessel viapositive nitrogen pressure a thoroughly mixed solution formed from 2.54g (0.0285 mol.) N,N-dimethylethanolamine and 20 ml of the recyclesolvent from above to which an additional 50 ml of aliquot of therecycle solvent was added with little if any mixing when combining insaid charge vessel. Next, 21.47 ml (0.0429 mole) 2.0 M n-butyllithiumfurther dissolved in 120 ml the recycle solvent was transferred to thecharge vessel and further combined with 50 ml of the recycle solvent(with little if any back mixing) from above. This unmixed solution wasthen pressure transferred over a period of 15 minutes to the stirred(800 RPM) reaction mixture under hydrogen. At the end of theorganolithium charge the agitation speed was increased to 1130 RPM andthe reactor pressure decreased from a peak pressure of 19 PSIG to anending pressure returning to 16 PSIG. During the course of the catalystformation the temperature increased 2-3° C. The reactor head space wasvented of 0 PSIG and then pressured to 45 PSIG with dry H₂ (through asubsurface feedline). The reactor was then heated to 72° C. with thepressuring building to 63 PSIG and further pressured to 72 PSIG. Theheating was conducted with 80° C. oil flowing through the reactorjacket—holding the reactor at 72° C. and 72 PSIG for 150 minutes beforeventing to 17 PSIG. The reactor was then heated to 80° C. with thepressure increased to 20 PSIG with 90° C. oil flowing through thereactor jacket. At the end of the 150 minute catalyst aging the RPMs wasadjusted to 960 time and styrene monomer feed was initiated, feeding1000.0 g (9.60 mol.) of styrene. The styrene was fed through asubsurface feed line (0.02″ ID tip) against the hydrogen head pressureof 15-17 PSIG over a period of 122 minutes controlling the reactiontemperature at 91° C. Within 10 minutes of initiation of the monomerfeed the reactor temperature reached 90.5° C. Periodically the hydrogenuptake was monitored by closing the valve to the regulator and timingthe period required to drop 5 PSIG. Thus the period in seconds requiredfor the pressure to drop (−1) one PSIG was recorded. When this value wasadjusted for estimated reactor headspace, the hydrogen uptake in termsof mole H₂ per mole of styrene feed appeared constant or near constant.At the end of the run the RPMs were adjusted to 975 and the hydrogenpressure increased to 18 PSIG.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous cyclohexane. The styrene feed and flush to the reactor wasdeemed complete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 300 ml of 5.13 g ofAcetic Acid dissolved in 300 g H₂O water and 300 recovered solventpreviously recovered from the initial solvent strip of a previous runs.Thus the reaction mixture was quenched with care in the wash reactor.The charge vessel and the reactor were then rinsed with 200 ml ofrecycle solvent and the rinse solution transferred to the wash reactorand combined with the crude quenched reaction mixture.

The above process was repeated as Example 73 with the identical chargesand conditions to within minor run to run variations in measuring outthe reagents with the exception that 911.3 g of styrene was fed over 111minutes against a hydrogen pressure of 14 PSIG, the catalyst componentswere combined with 500 RPM mixing instead of 800 RPMs. The reduction inthe amount of feed precluded the need to increase the RPMs or hydrogenpressure at the end of the feed. It is clear that the HMAPSdistributions produced were very similar except that Example 72 producea small amount of a high molecular weight composition at the end of thefeed.

During the transfer of the unquenched reaction mixtures (Examples 72 and73) 10 ml samples of the individual reaction mixtures were obtained foranalyses. The samples were slightly pink to water white—i.e. essentiallycolorless and transparent to light—with no settled or suspended solids.Any color was quenched by gently shaking/swirling or otherwisecontacting the mixtures with air. The samples were submitted for GPCanalysis without quenching the crude reaction mixtures. The GPC analysisexcluding ethylbenzene but including the dimer content was as follows:Example 72 M_(n): 485, M_(w): 747, M_(z): 1133, PD: 1.517, σ_(n)=356,_(n)α₃=2.462 and M_(w) 10% High=1965; Example 73 M_(n): 480, M_(w): 710,M_(z): 1009, PD: 1.421, σ_(n)=332, _(n)α₃=2.025; and M_(w) 10%High=1732.

The standard work-up from above provided 2270 g of solution. Wiped filmevaporation (WFE, 2″ glass Pope Still, operated at 50.0 mmHg vacuum,140° C., wiper speed 60% of full rate, feeding at 1.0 liters/hr)produced 1786.5 g HMAPS which was the further stripped (w/o analysis) ina second WFE operation (0.1-0.3 mmHg vacuum, 160° C., wiper speed 65% offull rate, feeding at 1.0 liters/hr) provided 1574 g of a HMAPSdistribution having 0.13 GPC area % styrene dimer content and a GPC MWDof M_(n): 591, M_(w): 817, M_(z): 1149, PD: 1.382, σ_(n)=365,_(n)α₃=2.285; and M_(w) 10% High=1998.

Upon completion of Examples 42 through 74 (a total of 32 runs) thereactor was rinsed with 1 liter of recycle solvent blown free oforganics with nitrogen and then opened for inspection. The reactor wasfound to be generally very clean with no polymer and only trace levelsof solids on the walls and surfaces at the level which marks the volumeof solvent used to form the catalyst. The reactor was wiped cleaned witha damp cloth and then with a cloth wetted with methanol. The monomer the0.02″ I.D. feed tip was replaced with one of equal length but having anI.D. of ≈0.45″. The reactor was sealed dried under stream of nitrogenwhile heating the jacket with 100° C. oil.

Examples 75-79

In all of these Examples (75 through 79) the catalyst was formed with500 RPM mixing with 18 to 21 PSIG hydrogen pressure with further agingat 72° C. and 72 PSIG hydrogen pressure for a period of between 200 and240 minutes. Examples 75 through 77 utilized the 0.045″ I.D. monomerfeed line tip 80° C. and 1130 RPM mixing, different styrene feed ratesand different recycle solvent charges and compositions. Of the threeruns, the HMAPS process of Example 77 was preferred. Example 78 utilizedthe 0.045″ I.D. styrene feed tip and fresh anhydrous methylcyclohexane(MCH) solvent, thus during this run there was no initial dilution of theorganolithium reagent with ethylbenzene. Upon completion of Examples75-78, the reactor was again flushed and purged of organics withnitrogen and opened for inspection. The reactor was found to be cleanand free of any solids at the line that marks the volume of the reactorduring catalyst formation. It is surmised that the lower RPMs employedduring catalyst formation may also bring the benefit of less splashingof the catalyst forming reaction mixture and thereby reduce thedeposition of catalyst components due to solvent flashing off theexposed and heated reactor surfaces. Upon completion of Examples 75-78the less preferred 0.045″ I.D. styrene feed tip was removed and replacedwith the preferred 0.02″ styrene feed tip and then prepared for thefinal run (Example 79) in this series. Example 79 which utilized acatalyst formed in MCH and ethylbenzene is described in greater detailbelow.

Examples 79 Representative of Full Scale Monomer Feed Volume for[DMEA⁻]₄Li₆H₂ Catalyst at 90° C. with Mixed Ethylbenzene andMethylcyclohexane Solvent

Anhydrous methylcyclohexane (MCH) solvent 220 of 320 ml (246.4 g) totalwas charged to the well rinsed reactor at 37.6° C. under a dry hydrogen(18 PSIG H₂) atmosphere. To the stirred solvent (500 RPM, four pitchedblade turbines with Configuration IV above) was charged through thecharge vessel via positive nitrogen pressure a thoroughly mixed solutionformed from 2.55 g (0.0286 mol.) N,N-dimethylethanolamine and 20 ml ofthe ethylbenzene to which an a 50 ml of aliquot of the MCH was addedwith little if any mixing when combining in said charge vessel. Next,21.52 ml (0.0430 mole) 2.0 M n-butyllithium further dissolved in 160 mlof anhydrous ethylbenzene was transferred to the charge vessel andfurther combined with 50 ml MCH with little if any back mixing. Thisunmixed solution was then pressure transferred over a period of 20.75minutes to the stirred (525 RPM) reaction mixture under hydrogen. At theend of the organolithium charge the agitation speed was increased to1050 RPM and the reactor pressure decreased from a peak pressure of 21PSIG to an ending pressure returning to 20 PSIG at 38.8° C. The reactorhead space was then pressured to 48 PSIG with dry H₂ (through asubsurface feedline). The reactor was then heated to 73.2° C. with thepressuring building to 59 PSIG and further pressured to 75 PSIG (60minutes having elapsed since completing the organolithium charge to thereactor). The heating was conducted with 80° C. oil flowing through thereactor jacket—holding the reactor at 73.9° C. and 75 PSIG for 205minutes before venting to 15 PSIG. Thus ca. 4 hours had passed since thestarting the charge of the organolithium reagent solution inethylbenzene to the reactor. At this time the mixing was adjusted to1130 RPMs time and styrene monomer feed was initiated, feeding 1023.9 g(9.83 mol.) of styrene. The styrene was fed through a subsurface feedline (0.02″ ID tip) against the hydrogen head pressure of 11-15 PSIGover a period of 113 minutes controlling the reaction temperature at82.5° C. Within 10 minutes of initiation of the monomer feed the reactortemperature reached 83.6° C. Periodically the hydrogen uptake wasmonitored by closing the valve to the regulator and timing the periodrequired to drop 5 PSIG. Thus the period in seconds required for thepressure to drop (−1) one PSIG was recorded. When this value wasadjusted for estimated reactor headspace, the hydrogen uptake in termsof mole H₂ per mole of styrene feed appeared constant or near constant.

At the end of the styrene feed, the monomer feed line to the reactor,including the alumina columns (basic alumina), were flushed with 50 mlof anhydrous MCH. The styrene feed and flush to the reactor was deemedcomplete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils. The unquenched polymerization reaction mixture wastransferred with positive H₂ pressure to the wash vessel previouslyheated (N₂ atmosphere) and previously charged with 400 ml of 6 g ofAcetic Acid and 14 g _(H2)SO4 dissolved in 380 g H₂O water and 300 ml offresh MCH. Thus the reaction mixture was quenched with care in the washreactor. The charge vessel and the reactor were then rinsed with 200 mlof recycle solvent and the rinse solution transferred to the washreactor and combined with the crude quenched reaction mixture.

During the transfer of the unquenched reaction mixture a 10 ml samplesof the reaction mixtures were obtained for analyses. The samples wereslightly pink to water white—i.e. essentially colorless and transparentto light—with no settled or suspended solids. Any color was quenched bygently shaking/swirling or otherwise contacting the mixtures with air.The samples were submitted for GPC analysis without quenching the crudereaction mixtures. The GPC analysis excluding ethylbenzene but includingthe dimer content was as follows: M_(n): 511, M_(w): 767, M_(z): 1096,PD: 1.429, σ_(n)=362, _(n)α₃=2.020 and M_(w) 10% High=1871.

The standard work-up from above provided 1000 g of solution. Wiped filmevaporation (WFE, 2″ glass Pope Still, operated at 50.0 mmHg vacuum,140° C., wiper speed 60% of full rate, feeding at 1.0 liters/hr)produced 961 g HMAPS having GPC analysis: M_(n): 542, M_(w): 804, M_(z):1142, PD: 1.483, σ_(n)=377, _(n)α₃=2.009 and M_(w) 10% High=1955. Asecond WFE operation (0.1-0.3 mmHg vacuum, 160° C., wiper speed 65% offull rate, feeding at 1.0 liters/hr) provided 871 g of a HMAPSdistribution having 1.3 GPC area % styrene dimer content and a GPC MWDof M_(n): 627, M_(w): 855, M_(z): 1163, PD: 1.364, σ_(n)=378,_(n)α₃=1.999; and M_(w) 10% High=1995.

HMAPS Distributions prepared from Examples 42-79 were brominatedaccording to the process technology of PCT Pub. No.: WO2010/127091 (U.S.Pat. No. 8,802,787 B2) to form brominated anionic chain transfervinylaromatic polymers (Br-ACTVAP). The average and standard deviationof the physical properties of these brominated polymers are listed belowas well as the properties of the Br-ACTVAP formed by combining and thenstripping the product distribution of Examples 14-15, that dimerstripped composition having M_(w)=731 and PD_(n)=1.38. The compositionswere further tested as polymeric flame retardants in high impactpolystyrene (HIPS) and were found to provide flame retarded (UL 94 VO at⅛″ and 1/16″) HIPS formulations with excellent overall propertiesincluding color (YI), Izod Impact, heat distortion temperature and VICATsoftening temperature.

Br-ACTVAP Of Examples Property 46 and 47 Average Stand. Dev. % Br (XRF)73.9 73.5 0.6 % Br (NMR) 73.8 73.9 0.4 Tg (° C.) 123.51 132.03 6.05Thermally Labile Bromine 305 156.72 74.76 (ppm at 300° C.) ColorSolution L 99.58 99.22 0.18 a −1.55 −1.73 0.26 b 4.02 4.89 0.75 Delta E4.33 5.19 0.77 COLOR Solids L 95.97 94.18 5.37 a −0.97 −0.78 0.15 b 4.164.26 0.32 Yellowness Index 7.03 7.48 0.46 Thermal Color (250° C.) DeltaE 14.45 15.06 1.93 TGA (nitrogen)  1% Wt. Loss (° C.) 341.08 341.74 5.44 5% Wt. Loss (° C.) 365.93 370.38 2.82 10% Wt. Loss (° C.) 376.22 379.025.67 50% Wt. Loss (° C.) 409.03 410.37 3.09 90% Wt. Loss (° C.) 450.7449.92 8.60 GPC (UV Detector) M_(n) 2167 2282 234 M_(w) 4078 3871 1002M_(z) 10437 8219 4343 PD_(n) 1.882 1.69 0.34

Comparative Examples

In the Comparative Examples 80-83 set forth below and demonstrated inFIGS. 12, 13 and 14 above, using prior art anionic chain transferpolymerization methods under nitrogen atmospheres where the chaintransfer agent is ethylbenzene with a potassium based catalyst, it isdemonstrated that these prior art technologies greatly suffer fromundesired competing polymerization steps leading to complex polymerchain distributions with different and less desired microstructures(i.e. the steps of the reaction pathways provided in FIGS. 1 and 2). InExamples 25-27, 39 and 40 we demonstrate that LOXKH, SASH and HASH,potassium and potassium with sodium based catalyst systems, the hydrogenmediated anionic chain transfer process technology of this invention,like the (hydrogen free) prior art technology produce complex multiplepolymer chain length distributions. The difference between suchpotassium and sodium based saline hydride process product distributioncompositions lies mainly in the different relative proportions of thedesired “head to tail” and undesired “tail to head to tail” andfragmentation microstructures.

Unpredictably and beneficially as is set forth in the Examples 1-24, 28,29 and 42-79, the process technologies of this invention that employ theLOXLiH and/or the LOXMgH₂ aggregates as the catalyst, provide greatlyimproved overall polymer microstructure. That is to say that the LOXLiHand the LOXMgH₂ catalyst produce polystyrene distributions comprisedalmost exclusively of oligomer chains of the most desired “head to tail”microstructure. Surprisingly these reagents and catalyst of thisinvention for all intents and purposes nearly eliminate all undesiredcompeting pathways and afford only chain transfer distributions of themost desired polymer microstructure (i.e. polymer structure 1 above) inranges of molecular weight distributions already proven to be useful informing polymeric products such as polymeric brominated flameretardants. Though we wish to not be bound by theory, under anionicchain transfer polymerization conditions when catalyst other than a theLOXLiH and/or the LOXMgH₂ is employed, significant competing sidereaction pathways give rise to added distributions of isomericoligomeric chains with different and undesired microstructures (see FIG.1). The isomerization pathway of FIG. 1 provides additional competingpathways which entail fragmentation/polymerization. Thesefragmentation/polymerization processes lead to: (A) oligomer chainstructures that have one more methyl (—CH₃) carbon (increase of 14Daltons); and/or (B) oligomer chain structures that have one less methyl(—CH₃) carbon (decrease of 14 Daltons, see FIG. 2). Such competingpolymerization reaction pathways are undesirable because they generallylead to quaternary carbon atoms in the polymer chain backbone (i.epolymermicrostructure). Such quaternary carbon atoms render a polymerdistribution as less compatible with aromatic electrophilic substitutioncatalyst which include either Brönstead acids (e.g. sulphonation) orLewis acids (e.g. halogenation).

Comparative Example 80 Isolation of Low Molecular Weight Oligomers fromComparative Example 46 of WO2010065468A8, an Ethylbenzene Chain TransferComposition of EPO 741147

A 150 ml sample of the water washed product mixture retained fromExample 46 of WO2010065468A8 was carefully concentrated at reducedpressure in a kugelrohr distillation apparatus. The cyclohexane solventand ethylbenzene chain transfer agent were distilled from the polymer toan ending condition of 150° C. in the kugelrohr oven and 1.0 mmHg vacuumin the bulb tube. The receiver with the solvent was removed and replacewith a fresh receiver, distillation was continued until a finaltemperature of 220° C. in the oven and <0.1 mmHg vacuum in the bulb tubethe distillation was continued until no evidence of a condensate in thereceiver could be perceived. The content of the receiver was dissolvedin methylene chloride and analyzed by gas chromatography. GC analysisindicated that 93% of the chains had the desired “head to tail”microstructure, with 3.4% of the chains having the undesired “tail tohead to tail” quaternary carbon linkage and 3.2% of the chains havingthe fragmented (FW_(i)−14) microstructure (See FIG. 12). The gaschromatogram in FIG. 12 also demonstrates large number of otherunidentified impurities oligomers present.

Comparative Example 81 Isolation of Low Molecular Weight Oligomers froman ACTVAP Composition of WO2008154453 w/ Oligomer MicrostructureAnalysis

An ACTVAP composition prepared from styrene wherein ethylbenzene insteadof toluene was used as the chain transfer agent. The anionic chaintransfer process was conducted in the 12-liter glass polymerizationreactor described in WO2008154453 in a like fashion of Example 8 of thatapplication. Thus 1905 g of styrene (18.29 mole) was fed (110 min, 70°C. rxn. temp.) to a reaction mixture formed in 4517.07 g (42.55 mole)from 13.74 g (0.1224 mole) potassium tert-butoxide, 71.51 g (0.6154mole) TMEDA, and 63.12 (0.1262 mole) of 2M n-butyllithium incyclohexane. After work-up and stripping of ethylbenzene (WFE 195° C.,60 mmHg) 2765.7 g of the ACTVAP was recovered having GPC MWD: M_(n):266, M_(w): 301, M_(z): 357, PD: 1.133. A second WFE operation (195° C.25 mmHg) yielded 2070 g of an ACTVAP composition having GPC MWD: M_(n):297, M_(w): 334, M_(z): 385, PD: 1.126. A third WFE operation (135° C.0.5 mmHg) on 1106 g of the 2070 g from the first yielded 909.25 g of acomposition essentially free of the major reaction product of theprocess, the mono-adduct of ethylbenzene to styrene (structurallyidentical to the head to tail styrene dimer). A fourth WFE operation(199.5° C., 0.12 mmHg) provided 449.02 g of a distillate. GC analysisindicated that 91% of the chains had the desired “head to tail”microstructure, with 8.9% of the chains having the undesired “tail tohead to tail” quaternary carbon linkage and 0.22% of the chains havingthe fragmented (FW_(i)−14) microstructure (See FIG. 13).

Comparative Example 82 Process Identical to Example 40 Except UnderNitrogen—No Hydrogen, w/ Oligomer Microstructure Analysis

Anhydrous ethylbenzene 256 g of 356 g (3.35 mole), was charged to thereactor and then heated to 65° C. under a dry nitrogen atmosphere. Tothe stirred solvent (1000 RPM, twin pitch blade impellers, bladeplacement Configuration I) was charged through the charge vessel asolution previously formed from 4.57 g (0.0407 mol.) potassiumt-butoxide, 44 g (0.41 mol.) ethylbenzene and 20.83 g (0.179 mol.) ofTMEDA. The charge vessel and transfer line to the reactor was flushedwith a 50 g portion of anhydrous ethylbenzene of the 356 g above. Next20.34 ml (0.0407 mole) 2.0 M n-butyllithium was transferred through thecharge vessel to the reactor followed by a 50 g aliquot of ethylbenzenefrom above. Agitation was maintained at 1045 RPMs while 800 g (7.68mol.) styrene was fed through a subsurface feed line (0.01″ ID tip, 5.2ft/s) against the nitrogen head pressure over a period of 183 minutescontrolling the temperature at 70° C. During the feed the reactorpressure increased from 0 PSIG to 4 PSIG which was then vented back to 0PSIG and consequently for the rest of the feed the reactor was vented tothe mineral oil bubbler. At the end of the styrene feed, the monomerfeed line to the reactor, including the alumina columns, were flushedwith 50 ml of anhydrous cyclohexane. The styrene feed and flush to thereactor was deemed complete when no further heat of reaction wasobserved generally signified by the permanent closing of the automatedcontrol valve on the coiling coils.

The unquenched polymerization reaction mixture was transferred withpositive N₂ pressure to the wash vessel previously heated (N₂atmosphere) and previously charged with 300 ml of deoxygenated wateralong with 500 ml of cyclohexane. During the transfer of the unquenchedreaction mixture a 10 ml sample of the reaction mixture is obtained foranalysis. The sample is dark black-red (black cherry) in color and nottransparent to light typical of all other ACTVAP and ACTSP processespreviously observed. The sample was quenched by the addition of a dropof methanol which immediately quenches the dark red color without theformation of a gas. GPC Analysis of the crude quenched reaction mixturewas as follows: M_(n): 567, M_(w): 908, M_(z): 1331, PD: 1.601,σ_(n)=440, _(n)α₃=2.048.

The standard work-up and solvent strip recited above provided 1240.2 gof solution. Wiped film evaporation (WFE, 2″ glass Pope Still, operatedat 50.0 mmHg vacuum, 140° C., 60% of full wiper speed, feeding at 1.0liters/hr) produced 943.1 g of an ACTVAP distribution having GPC MWD ofM_(n): 580, M_(w): 904, M_(z): 1286, PD: 1.559, σ_(n)=433, _(n)α₃=1.868.A second WFE operation (0.1-0.3 mmHg vacuum, 172.5° C., 60% of fullwiper speed, feeding at 1.0 liters/hr) provided 849.4 of an ACTVAPdistribution having 0.70 GPC area % styrene dimer content and a GPC MWDof M_(n): 707, M_(w): 976, M_(z): 1306, PD: 1.380, σ_(n)=436,_(n)α₃=1.741. Thus the conditions of this Comparative Example and thatof Example 40 are identical except for the atmosphere employed. Clearlythe hydrogen mediation of Example 40 greatly improved the chain transferefficiency and provided a MWD with much lower values for M_(n), M_(w)and M_(z). A third WFE operation was performed to obtain the lowmolecular weight oligomers in order to determine the ACTVAP distributionmicrostructure. Thus a 131.2 g sample of the 849.4 g productdistribution recovered from the 2^(nd) WFE operation was stripped ofoligomers 0.1 mmHg vacuum, 199.5° C., wiper speed 85% of full rate,feeding at 2.0 g/min.). This third WFE operation produced 19.07 g of astyrene oligomer mixture having MWD: of M_(n): 318, M_(w): 338, M_(z):357, PD: 1.061. GC analysis indicated that 93% of the chains had thedesired “head to tail” microstructure, with 5.0% of the chains havingthe undesired “tail to head to tail” quaternary carbon linkage and 2.3%of the chains having the fragmented (FW_(i)−14) microstructure (See FIG.14).

Comparative Example 83 Process Identical to Example 40 Except UnderNitrogen and Comparative Example 43 w/ No Hydrogen but Usingn-Propylbenzene w/ Oligomer Microstructure Analysis

Anhydrous n-propylbenzene 281 g of 381 g (3.18 mole), was charged heatedto the reactor and then to 65° C. under a dry nitrogen atmosphere. Tothe stirred solvent (1130 RPM, twin pitch blade impellers, bladeplacement Configuration I) was charged through the charge vessel asolution previously formed from 4.61 g (0.0411 mol.) potassiumt-butoxide, 50 g (0.42 mol.) n-propylbenzene and 26.34 g (0.179 mol.) ofTMEDA. The charge vessel and transfer line to the reactor was flushedwith a 50 g portion of anhydrous n-propylbenzene of the 381 g above.Next 20.32 ml (0.0407 mole) 2.0 M n-butyllithium was transferred throughthe charge vessel to the reactor followed by a 50 g aliquot ofn-propylbenzene from above. Agitation was maintained at 1131 RPMs while804 g (7.72 mol.) styrene was fed through a subsurface feed line (0.01″ID tip, 5.2 ft/s) against the nitrogen head pressure over a period of183 minutes controlling the temperature at 70° C. During the styrenemonomer feed the reactor pressure increased from 0 PSIG to 9 PSIG. Atthe end of the styrene feed, the monomer feed line to the reactor,including the alumina columns, were flushed with 50 ml of anhydrouscyclohexane. The styrene feed and flush to the reactor was deemedcomplete when no further heat of reaction was observed generallysignified by the permanent closing of the automated control valve on thecoiling coils.

The unquenched polymerization reaction mixture was transferred withpositive N₂ pressure to the wash vessel previously heated (N₂atmosphere) and previously charged with 300 ml of deoxygenated wateralong with 500 ml of cyclohexane. During the transfer of the unquenchedreaction mixture a 10 ml sample of the reaction mixture is obtained foranalysis. The sample is dark black-red (black cherry) in color and nottransparent to light typical of all other ACTVAP and ACTSP processespreviously observed. The sample was quenched by the addition of a dropof methanol which immediately quenches the dark red color without theformation of a gas. GPC Analysis of the crude quenched reaction mixturewas as follows: M_(n): 668, M_(w): 1013, M_(z): 1354, PD: 1.517,σ_(n)=480, _(n)α₃=1.413.

The standard work-up and strip from above produced 1908.2.2 g ofsolution. Wiped film evaporation (WFE, 2″ glass Pope Still, operated at50.0 mmHg vacuum, 140° C., 60% of full wiper speed, feeding at 1.0liters/hr). This first WFE operation produced 939.88 g of an ACTVAPdistribution having GPC MWD of M_(n): 690, M_(w): 1017, M_(z): 1336, PD:1.475, σ_(n)=475, _(n)α₃=1.992. A second WFE operation (0.1-0.3 mmHgvacuum, 172.5° C., 60% of full wiper speed, feeding at 1.0 liters/hr)provided 866.04 of an ACTVAP distribution having 0.70 GPC area % styrenedimer content and a GPC MWD of M_(n): 785, M_(w): 1066, M_(z): 1353, PD:1.358, σ_(n)=470, _(n)α₃=1.245. Thus the conditions of this ComparativeExample and that of Comparative Example 43 are identical except for thechain transfer agent employed and thus the compositions in terms oftheir MWD are nearly identical.

A third WFE operation was performed to obtain the low molecular weightoligomers in order to determine the ACTVAP distribution microstructure.Thus a 161.4 g sample of the 866.04 g product distribution recoveredfrom the 2^(nd) WFE operation was stripped of oligomers 0.1 mmHg vacuum,199.5° C., wiper speed 85% of full rate, feeding at 2.0 g/min.). Thisthird WFE operation produced 16.33 g of the ACTVAP oligomer mixture. GCanalysis indicated that 99.08% of the chains had the desired “head totail” microstructure (See FIG. 9).

Thus it is clear from these three Comparative Examples (41-43) thatprior art compositions that rely on ethylbenzene as a chain transferagent in their formation suffer from both chain isomerization reactionsthat lead to the formation of added distributions of polymer chains withundesired microstructures. The results presented in the ComparativeExamples and in the LOXKH, SASH and HASH Examples of this inventionindicate that this undesired pathway as laid out in FIG. 1 and FIG. 2 ispromoted by potassium and by sodium. Quite surprisingly and beneficiallythe LOXLiH and LOXMgH₂ Examples of this invention clearly indicate thatthe reaction pathways of FIGS. 1 and 2 are greatly suppressed and forall intents and purpose even eliminated when these novel catalyst ofthis invention are employed in the hydrogen mediated saline hydrideinitiated polymerizations processes also of this invention.

It is important to note that the undesirably high levels—greater than 3%of the polymer chains—of quaternary carbons only results when thepolymer chain initiating species is an α-methylbenzyl anion ArC(R)H⁻(where R=CH₃) whether formed from ethylbenzene or formed from fromstyrene. For the anion ArC(R)H⁻ where R=H (i.e. initiator formed from amethylbenzene e.g. toluene) it is structurally impossible to form aquaternary carbon linkage no matter how frequently a pathway analogousto FIG. 1 takes place. As Comparative Example 44 demonstrates, for theanion ArC(R)H⁻ when R is alkyl group bigger than CH₃ (e.g. CH₂CH₃ as inExample 40) and likewise inductively a better electron donor than CH₃,then the pathways of FIGS. 1 and 2 are reduced significantly andconsequently compositions having less than 3% even less than 1% of thechains with quaternary carbon linkage can result. This should be clearby inspection of the following structures below.

As can now be explained in the light of the discoveries of thisinvention, it should be further understood that the isomerizationreaction—backbiting pathway—of FIG. 1 essentially only occurs for theliving trimer of styrene. One of ordinary skill in the art wouldrecognize that the backbiting pathway involving a living styrenetetramer, pentamer, hexamer etc. etc. would force a phenyl group or thepoly(styryl) chain into a disfavored position and hence backbiting issuppressed. This should be clear from the chemical structures depictingthe living pentamers above. Accordingly the extent of undesired chainisomerization reaction arising from backbiting or intramolecular protontransfer is dictated by stereo electronic effects. The transition stateor activated complex involves 6 atoms (5 carbons and one proton) and issuppressed when the group alpha to the proton to be transferred is largeand a stronger electron donor. Surprisingly the nature of the cationassociated with the anion has a dramatic effect on the proton transferreaction. Thus the intramolecular proton transfer of the living trimeris greatly suppressed by magnesium and essentially eliminated by lithiumas compared to other alkali and alkaline earth metals. Accordingly,sodium, potassium and all other Group 1 and Group 2 metals promote theundesired intramolecular proton transfer and this backbiting reactionproduces composition with less desired polymer microstructure. This isparticularly problematic when forming compositions from eitherethylbenzene in combination with styrene, or from styrene alone.

Ethylbenzene is an ineffective chain transfer agent when using lithiumbased chain transfer catalyst (e.g. catalyst formed form ethylbenzene,butyllithium and TMEDA, Table I above Example D from EP O 741 147).However the novel monometallic lithium and the novel bimetallic lithiumand magnesium catalysts used in combination with the novel hydrogenmediated saline hydride initiated polymerization process of thisinvention, afford for the first time anionic chain transfer polystyrenedistributions free of an added organic chain transfer agent and havingvery high—greater than 97% even greater than 99.2%—of the desired “headto tail” polymer microstructure and incorporating essentially no otherinitiating species other than a hydride ion—such microstructureintegrity that is necessary for further derivatization via aromaticelectrophilic substitution reactions of polystyrene compositions.

Analytical Methods

Molecular weight distributions in terms of M_(w), M_(n), M_(z), PD andM_(w) 10% High values for low molecular weight (M_(w)<1600 Daltons) wereobtained by GPC using a Viscotek TDA modular system equipped with a UVdetector, autosampler, pump, and temperature controlled columncompartment. The columns used were Agilent Oligopore columns, 300 mm by7.5 mm, part number 1113-6520. The solvent used was tetrahydrofuran,HPLC grade. The test procedure used entailed dissolving approximately0.06-0.1 g of sample in 10 mL of THE. An aliquot of this solution isfiltered and 2004, is injected on the columns. Based on isolated1,3-diphenylbutane (dimer) and 1,3,5-triphenylhexane (trimer) adducts,and the mode of separation is size exclusion, peaks are identifiedaccording to their order of elution as 1,3-diphenylbutane,1,3,5-triphenylhexane, 1,3,5,7-tetraphenyloctane (tetramer),1,3,5,7,9-pentaphenyldecane (pentamer), etc. The individual peaks of theoligomeric material are then assigned theoretical molecular weightvalues. A calibration curve is constructed using these theoreticalvalues and their corresponding retention times. Based on thiscalibration, the overall distribution data is calculated and reported.The calculations were performed by the Viscotek Omnisec, version4.2.0.237 gel permeation chromatography (GPC) data collection andprocessing system.

Molecular weight distributions in terms of M_(w), M_(n), M_(z) and PDvalues for higher molecular weight (M_(w)>1600 Daltons) were obtained byGPC using a Viscotek TDA modular system equipped with a UV detector,autosampler, pump, and temperature controlled column compartment. Thefollowing three Agilent Technologies columns were used in series toperform the separation: (1) Oligopore column, 300 mm by 7.5 mm, partnumber 1113-6520, (1) Mixed Bed E, 300 mm×7.5 mm, part number 1110-6300,and (1) Mixed Bed D, 300 mm×7.5 mm, part number 1110-6504. The solventused was tetrahydrofuran, HPLC grade. The test procedure used entaileddissolving approximately 0.06-0.1 g of sample in 10 mL of THE. Analiquot of this solution is filtered and 2004, is injected on thecolumns. Based on isolated 1,3-diphenylbutane(dimer) and1,3,5-triphenylhexane (trimer) adducts, and the mode of separation issize exclusion, peaks are identified according to their order of elutionas 1,3-diphenylbutane, 1,3,5-triphenylhexane, 1,3,5,7-tetraphenyloctane(tetramer), 1,3,5,7,9-pentaphenyldecane (pentamer), etc. The individualpeaks of the oligomeric material are then assigned theoretical molecularweight values. A calibration curve is constructed using thesetheoretical values and their corresponding retention times along withthe retention times of polystyrene reference standards of knownmolecular weight. Based on this calibration, the overall distributiondata is calculated and reported. As above the calculations wereperformed by the Viscotek Omnisec, version 4.2.0.237 gel permeationchromatography (GPC) data collection and processing system.

The gas chromatography method and conditions for analyses of lowmolecular styrene oligomers (dimers thru hexamers) was as follows.Styrene oligomeric mixtures obtained from wiped film distillation and/orkugelrohr distillation from the product resin were analyzed using aHewlett Packard HP 6850 gas chromatograph equipped with an AgilentTechnologies DB-530 meter, 0.25 mm I.D., 0.25 μm column. Oligomersamples were prepared as 2.5 wt % solutions in methylene chloride andmanually injected (injection temperature of 270° C.), separated using atemperature program with a helium carrier gas and response measuredusing a flame ionization detector. The temperature program was asfollows: a) 100° C. initial temperature w/ 2 min hold w/ carrier gasflow rate of 1.5 ml/min; b) programed temperature rise to 300° C. at 8°C./min w/ carrier gas flow rate of 2.0 ml/min; c) 10.0 min hold ant 300°C. w/ carrier gas flow rate of 2.0 ml/min; d) programed temperature riseto 320° C. at 3.0° C./min w/ carrier gas flow rate of 2.0 ml/min; and e)15.0 min hold at 320° C. w/ carrier gas flow rate of 2.0 ml/min. Datawas collected and analyzed using Atlas 8.2.3 chromatography data system.Microstructure assignment was made based on isolated standards ormixtures of standards for the oligomers grouped based on the number ofstyrene monomer units (i.e dimers separate from trimers separate fromtetramers separate from pentamers separate from hexamers) incorporatedin the oligomer microstructure and normalized based on total area countsfor said group. Additionally oligomer mixtures were analyzed by massspectrometry to further confirm assignment of oligomer structures formedfrom the competing undesired fragmentation polymerization process ofFIGS. 1 and 2 above (i.e discrete oligomer with FW_(i)=[i(104)+2−14]Daltons as well as a discrete oligomer with FW_(i)=[i(104)+2+14] where iis the number of: 1) styrene monomer units; or 2) is the number ofaromatic rings for an ethylbenzene styrene chain transfer polymerizationproduct; incorporated in the discrete oligomer chain of interest). As isdemonstrated in FIGS. 3-17, it is clear and unequivocal from theapplication of this GC method of microstructure analysis thatcompositionally related yet quite different prior art technologiesprovide compositions with drastically dissimilar and undesirable amountsof oligomeric microstructures for the first six discrete oligomerstructures. Furthermore this technique of analyzing the dimers thruhexamers product mixture, especially the trimeric and tetramericoligomers, is deemed to be predictive of the microstructure integrity orpurity of entire polymeric distribution. Thus it is deemed sufficientthat the microstructure purity of the entire distribution can beestablished by this oligomer analyses. Thus the preferred LOXSH PS andHMAPS compositions are easily differentiated from prior art compositionsby the oligomer test whether the GC analyses is conducted over the first5 (dimers through hexamers) oligomers or only the trimers and tetramers.Such microstructure purity is deemed to be a superior advantage over theprior art and is an advancement in forming polystyrene compositionsdeemed as polymeric by the OECD definition of a polymer and comprisedessentially if not solely of styrene monomer.

Determination of Empirical Formula for Catalyst and Reagent Compositionsof this Invention

As mentioned above the complications brought on by the degree ofassociation of alkyllithium compound as initiators as well as mixedorganometallic as initiators for living anionic polymerization reactionsof styrene and conjugated dienes is well established in the art (in thisconnection see Hsieh H. L. and Quirk, R. P. Anionic PolymerizationPrinciples and Practical Applications, Marcel Dekker, 1996, New York, pp135-132 especially Table 6.2 pg. 138). The degree of association ofn-butyllithium is generally 6 wherein the degree of association oft-butyllithium and sec-butyllithium is generally 4 in hydrocarbonsolvents. Thus only one in six n-butyllithium agents in the aggregate ofthe associated alkyllithium compound initiates living polymerization;one in four for both sec-butyllithium and t-butyllithium. A concept ofthis invention is that by analogy only one hydride per aggregate of thecatalyst composition will initiate anionic polymerization. Thus theinverse ratio of the number of polymers formed to the number ofaggregates that in theory could be formed under living anionicpolymerization, should provide evidence for the average constitutionalcatalyst compositions of this invention.

As was mentioned above, the only two known hydrocarbon soluble lithiumhydride reagents existed as aggregates having the molecular formulae[(t-BuOLi)₁₆(LiH)₁₇] for the super aggregate formed viaphoto-degradation and [(DipNPPh₂)₄Li₈H₄] (Dip, 2,6-iPr₂C₆H₃) for Stash'shydrocarbon soluble LiH complex. In both cases the molecular formulaewere determined by isolation and x-ray crystallography. The catalystcompositions of this invention are not of necessity isolated such thatx-ray crystallography or say combustion analyses or other modern methodof chemical analyses can be conducted. The term empirical formula ascommonly used in the art is a chemical formula in which the subscriptsare the smallest integers that give the ratio of atoms in one molecule.Here, however, we define “empirical formula” as the chemical formula ofthe constituents as the whole number ratio of the polarizing complexingagent(s), the saline metal(s) and the total ionic hydride present in thecatalyst composition. Furthermore the catalyst composition is taken asthe constituent composition of the catalysts aggregates wherein eachaggregate will initiate only one living anionic polystyrene chain.

The catalyst compositions of this invention in terms of theirconstituents are known because: (1) well understood and wellcharacterized reagents are used in forming the catalyst compositions;and (2) the relative charge ratios clearly define the catalyst reactionmixture in terms of (a) the relative ratios of the polarizing complexingagent(s), (b) the saline metal(s) and (c) the active metal alkyl andhence the total ionic hydride present. However the state of aggregationof the catalyst(s) cannot be known simply based on these simple chargeratios of known components. A simple test to determine the average or inthis context “empirical formula” (as defined in this context above) ofthe catalyst aggregate composition has been devised. This test entailsthe application of the catalyst as reagents as initiators for livinganionic polymerization of styrene (APS) under inert hydrogen freeatmosphere (i.e. free of all forms of chain transfer, Examples 33-37).The ratio of the number average molecular weight of the resulting APSdistribution (M_(n APS)) is then related to the theoretical numberaverage molecular weight M_(n-Th). Wherein M_(n-Th)≈104*[mole of styrenecharged]/[total mole of hydride formed] and wherein each mole of hydrideformed is equal to the total equivalents of active lithium alkyl andactive magnesium alkyl from which the hydride is formed (wherein anactive lithium alkyl provides one equivalent and an active magnesiumalkyl provides two equivalents). To illustrate this analytical techniqueExample 36 is reviewed. In Example 36 a catalyst was formed from acharge ration that entails 1 mole of dimethylethanolamine, 2 moles ofn-butyllithium and 1 mole of hydrogen. Thus this catalyst formingreaction would produce a catalyst composition having the chemicalformula [DMEA⁻]Li₂H. To this catalyst composition was charged styrene(10.5 mole) which is 21 mole relative to the amount of lithium hydridepresent in the catalyst and hence M_(n-Th)≈104*21≈2184 Daltons. Howeverthe M_(n APS) determined experimentally was 8447 and accordinglyM_(n APS)/M_(n-Th)=8447/2184=3.9≈4. Based on this it is concluded thatan aggregate comprised of [DMEA⁻]₄Li₈H₄ was formed in the reactionmixture and only one of the hydride present in the aggregates initiatesliving anionic polymerization of styrene under an inert atmosphere. Thisempirical formula [DMEA⁻]₄Li₈H₄ compares well with the molecular formula[(DipNPPh₂)₄Li₈H₄] obtained by x-ray crystallography by Stasch for hisaggregate formed from one mole of the bulky phosphinous amide ligandDipNHPPh₂, 2 mole of sec-butyllithium, and phenylsilane. Thus in fact bysimple analogy to Stasch's hydrocarbon soluble LiH complex and theapplication of this test method, strong evidence exist that theempirical formula [DMEA⁻]₄Li₈H₄ is in fact the molecular formula for atleast a portion of the catalyst composition aggregates of Example 36. Itis pointed out that the lowest whole number ratio for [DMEA⁻]₄Li₈H₄ is[DMEA⁻]Li₂H, however this formula brings with it little informationabout the catalyst aggregate composition(s) as they are used in thepractice of this invention. It is also pointed out that the practitionerof this invention when desired may use multiple polarizing complexingagents such that the aggregates formed are comprised for example as[PCA⁻]₄Li₈H₄ wherein each [PCA⁻] is independently the same or different.

TABLE III LOXLiH catalyst small scale screening Examples with ca. 1/4styrene monomer feed. Example 1 2 3 4 5 Temp Catalyst Formed, ° C. 20-2423 25-27 30-32 31-48 Temperature, ° C. 80 80 80 80 80 Hydrogen, psig 5 613 13 13 Solvent EB EB CH CH CH Mass, g 434.2 434.2 384.9 384.9 384.9Ethylbenzene moles 4.09 4.09 0.00 0.00 0.00 DMEAH (g) 2.36 1.22 2.272.30 2.30 moles 0.0265 0.0137 0.0255 0.0258 0.0258 Ethylbenzene (g) 71.5139.5 134.7 135.01 135.01 moles 0.67 1.32 1.27 1.27 1.27 vol, ml 82 161155 156 156 TMEDA (g) 12.13 6.31 12.22 6.50 3.25 moles 0.104 0.054 0.1050.056 0.028 vol, ml 15.65 8.14 15.77 8.39 4.19 n-Butyllithium, M 2.0 2.02.0 2.0 2.0 vol, ml 28.82 15.03 30.37 27.11 28.77 moles 0.0576 0.03010.0607 0.0542 0.0575 Styrene (g) 240 247.7 257.2 258 263 moles 2.30 2.382.47 2.48 2.53 vol, ml 264 272 283 284 289 feed rate ml/min 7.50 7.967.50 7.00 7.00 time of feed, min 35 34 38 41 41 feed rate g/min 6.827.24 6.82 6.36 6.36 feed velocity ft/sec 2.02 2.15 2.02 1.89 1.89Process Scale-Up Parameters 2.18 2.20 2.38 2.10 2.23 mole organolithium/mole DMEAH Mole TMEDA/mole LiH* 3.35 3.32 2.98 1.03 0.486 Initial LiH*conc. ppm 457 220 499 408 457 Initial LiH* conc., M 0.0500 0.0240 0.05030.0411 0.461 Final LiH* conc. ppm 317 155 345 278 308 Final LiH* conc.,M 0.034 0.017 0.034 0.028 0.031 mole styrene/mole LiH* 73.9 145.3 342278 309 mole sty/hr/mole LiH* 126.0 254.6 111.4 129.0 115.5 molestyrene/mole of EB 0.48 0.44 1.94 1.94 1.98 mole styrene/hr/mole of EB0.82 0.77 3.09 2.88 2.88 Solvent stripped polymer yield (g) 200.4 222.0245.0 487.5 yield % on monomer 83.5% 89.6% 95.3% 93.6% M_(n) 416 486 702565 M_(w) 579 693 1091 851 M_(z) 794 949 1489 1177 PD_(n) 1.392 1.4261.554 1.506 σ_(n) 260 317 523 402 _(n)α₃ 1.961 1.822 1.537 1.719 Dimerstrip. polymer yield (g) 152.0 181.3 217.9 427.2 yield % on monomer63.3% 73.2% 84.7% 82.0% M_(n) 529 600 821 676 M_(w) 670 769 1152 920M_(z) 856 983 1505 1210 PD_(n) 1.267 1.282 1.403 1.361 σ_(n) 273 318 521406 _(n)α₃ 1.815 1.704 1.417 1.629

TABLE IV LOXLiH catalyst process Examples with ca. 1/2 styrene monomerfeed without use of a promotor (i.e. TMEDA free). Example 6 7 8 9 10 1112 13 Temp Catalyst Initially 20 34 40 40 55 40 40 35 Formed (° C.) Rxn.Temperature (° C.) 80 80 80 80 80 80 80 80 Hydrogen (psig) 59-31 59-3165-31 17-36 15-17 15 15 15 Cyclohexane (g) 311.6 311.6 311.6 311.6 311.6311.6 311.6 311.6 vol. (ml) 400 400 400 400 400 400 400 400 DMEAH (g)2.34 2.38 3.40 3.42 2.37 4.60 4.60 4.60 moles 0.0263 0.0267 0.03810.0384 0.0266 0.0516 0.0516 0.0516 Ethylbenzene (g) 106.00 106.00 106.00110.00 120.00 100.00 100.00 100.00 moles 1.00 1.00 1.00 1.04 1.13 0.940.94 0.94 vol. (ml) 122 122 122 127 138 115 115 115 n-Butyllithium, M2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 vol. (ml) 28.59 29.25 28.59 29.23 20.2839.28 39.02 38.87 moles 0.0572 0.0585 0.0572 0.0585 0.0406 0.0786 0.07800.0777 Styrene, g 447.0 452.6 471.0 519.5 546.5 512.8 406.2 219.5 moles4.29 4.35 4.52 4.99 5.25 4.92 3.90 2.11 vol. (ml) 492 498 518 572 601564 447 241 feed rate (ml/min.) 7.00 5.00 5.00 5.00 5.00 7.00 5.57 4.00time of feed (min.) 70.2 99.6 103.6 114.3 120.2 80.6 80.2 60.4 feed rate(g/min.) 6.36 4.55 4.55 4.55 4.55 6.36 5.06 3.64 feed velocity (ft/sec.)1.89 1.35 1.35 1.35 1.35 1.89 1.50 1.08 Process Scale-Up Parameters moleorganolithium/mole 2.18 2.19 1.50 1.52 1.53 1.52 1.51 1.51 DMEAH InitialLiH* conc. M 0.056 0.058 0.035 0.036 0.025 0.049 0.048 0.047 InitialLiH* conc. ppm 556 571 342 357 247 480 471 465 Final LiH* conc. ppm 277282 166 165 112*  223 247 312 Final LiH* conc., M 0.028 0.029 0.0170.017 0.011* 0.023 0.025 0.032 mole styrene/mole LiH* 138.8 136.7 237.5248.1 375.3 182.7 147.5 80.7 mole sty/hr/mole LiH* 118.5 82.4 137.5130.3 187.3 136.0 110.3 80.2 mole styrene/mole of EB 4.29 4.35 4.52 4.814.64 5.22 4.13 2.23 mole styrene/hr/mole of EB 3.67 2.62 2.62 2.52 2.313.89 3.09 2.22 M_(n calc)  14,433 14,217 24,706 25,808 39,037 18,999 15,343 8390 % Efficiency M_(n calc)/ 3600%   4000%   6640%   6520%  8070%   5280%   4420%   2640%   M_(n)) · 100% Solvent stripped polymer777 1306 910 yield (g) yield % on monomer 86.4% 85.0% 79.9% M_(n) 402356 372 396 484 360 347 318 M_(w) 564 476 513 601 4722 506 462 408 Mz809 663 728 1002 38108*    746 641 545 PD_(n) 1.434 1.393 1.419 1.6678.070 1.474 1.387 1.336 σ_(n) 255 207 229 285 1432 229 200 169 _(n)α₃2.402 2.447 2.407 3.456 28.594* 2.695 2.438 2.323 Dimer strip. polymeryield 575.34 1015.71 606.32 (g) yield % on monomer 64%  66%  53%  M_(n)519 578 494 M_(w) 639 2556 602 M_(z) 826 31565 761 PD_(n) 1.231 4.4221.219 σ_(n) 250 1069 231 _(n)α₃ 2.391 36.368* 2.166 *Hydrogen uptakebecame exceedingly slow during the last 25 minutes of monomer feedconsequently a high molecular weight tail formed as part of the MWD.

TABLE V LOXLiH catalyst process w/full styrene monomer feed withpromotor (i.e. TMEDA) in cyclohexane. Example 14 15 16 17 18 19 TempCatalyst Initially Formed 37 37 37 37 8 8 Temperature, ° C. 80 80 80 8080 80 Hydrogen (psig) 16 12 19 21 13 13 Cyclohexane (g) 233.7 233.7350.6 428.5 233.7 233.7 vol, ml 300 300 450 550 300 300 DMEAH (g) 2.722.68 2.51 3.60 1.42 1.69 moles 0.0305 0.0301 0.0281 0.0404 0.0159 0.0190Ethylbenzene (g) 140.00 140.00 82.00 60.00 140.0 140.0 moles 1.32 1.320.77 0.57 1.32 1.32 vol, ml 161 161 95 69 161 161 TMEDA (g) 1.82 1.782.47 3.55 3.70 3.30 moles 0.0157 0.0153 0.0213 0.0306 0.032 0.028 vol,ml 2.35 2.30 3.19 4.58 4.77 4.26 n-Butyllithium, M 2.0 2.0 2.0 2.0 2.02.0 vol, ml 22.90 22.68 21.18 30.38 23.98 23.71 moles 0.0458 0.04540.0424 0.0608 0.0480 0.0474 Styrene, g 960.4 1020.4 780.0 668.0 953.5963.5 moles 9.22 9.80 7.49 6.41 9.16 9.25 vol, ml 1057 1123 858 735 10491060 feed rate ml/min 7.00 7.00 7.00 7.00 7.00 7.00 time of feed, min151 160 123 105 150 151 feed rate g/min 6.36 6.36 6.36 6.36 6.36 6.36feed velocity ft/sec 1.89 1.89 1.89 1.89 1.89 1.89 Process Scale-UpParameters mole organolithium/mole DMEAH 1.50 1.51 1.50 1.50 3.01 2.50Mole TMEDA/mole LiH 1.02 1.00 1.50 1.50 0.99 1.00 Initial LiH* conc. M0.0314 0.0314 0.0250 0.0311 0.0653 0.0581 Initial LiH* conc., ppm 307307 249 312 641 570 Final LiH* conc. ppm 90 86 91 136 188 166 Final LiH*conc. M 0.009 0.009 0.009 0.014 0.019 0.017 mole styrene/mole LiH* 603.4640.6 527.4 314.8 285.8 325.1 mole sty/hr/mole LiH* 239.9 239.7 258.1179.9 114.4 128.8 mole styrene/mole of EB 6.98 7.42 9.68 11.33 6.93 7.00mole styrene/hr/mole of EB 2.78 2.78 4.74 6.48 2.78 2.78 M_(n calc)62,755 66,627 54,847 32,740 29728 33808 % Efficiency (Mn calc/Mn) · 100%14,295%   15,567%   13576%  7908%   6710%   7900%   Solvent strippedpolymer yield (g) 1793 1309 1744 yield % on monomer 90.5% 90.4% 91.0%M_(n) 439 428 404 414 443 428 M_(w) 628 636 561 577 664 613 M_(z) 886979 778 804 1040 881 PD_(n) 1.411 1.539 1.387 1.393 1.566 1.437 σ_(n)288 298 252 260 313 281 _(n)α₃ 2.108 2.778 2.098 2.127 2.901 2.292 Dimerstrip. polymer yield (g) 1492 1076 1452 yield % on monomer 75.3% 74.3%75.8% M_(n) 530 500 551 M_(w) 731 647 747 M_(z) 1150 848 1109 PD_(n)1.379 1.294 1.356 σ_(n) 326 271 329 _(n)α₃ 3.661 1.961 3.118

TABLE VI LOXLiH catalyst process with full styrene monomer feed withpromotor (i. e. TMEDA) in methylcyclohexane (MCH). Example 20 21 22 2324 Temp Catalyst Initially Formed −5 −5 −5 −5 −5 Temperature, ° C. 80 8080 80 80 Hydrogen (psig) 14 20 to 15 25 15 13 Methylcyclohexane (g)231.0 231.0 231.0 231.0 231.0 vol, ml 300 300 300 300 300 DMEAH (g) 1.001.00 1.35 1.35 2.27 moles 0.0112 0.0112 0.0151 0.0151 0.0255Ethylbenzene (g) 140.0 140.0 140.0 140.0 140.0 moles 1.32 1.32 1.32 1.321.32 vol, ml 161 161 161 161 161 TMEDA (g) 2.60 2.60 3.53 3.53 12.40moles 0.022 0.022 0.030 0.030 0.107 vol, ml 3.35 3.35 4.55 4.55 16.00n-Butyllithium, M 2.0 2.0 2.0 2.0 2.0 vol, ml 16.81 16.81 22.73 22.7330.79 moles 0.0336 0.0336 0.0455 0.0455 0.0616 Styrene, g 1042.5 255.0949.9 930.0 1041.0 moles 10.01 2.45 9.12 8.93 10.00 vol, ml 1147 2811045 1023 1145 feed rate ml/min 7.00 7.00 7.00 7.00 7.00 time of feed,min 164 40 149 146 164 feed rate g/min 6.36 6.36 6.36 6.36 6.36 feedvelocity ft/sec 1.88 1.88 1.88 1.88 1.88 Process Scale-Up Parameters3.00 3.00 3.00 3.00 2.42 mole organolithium/mole DMEAH Mole TMEDA/moleLiH 1.00 1.00 1.00 1.00 2.95 Initial LiH* concentration, M (moles/liter)0.0465 0.0465 0.0620 0.0620 0.0711 Initial LiH* conc., ppm 459 459 612612 701 Final LiH* concentration, 0.013 0.028 0.018 0.018 0.020 Molarity(moles liter) Final LiH* conc., ppm 124 277 179 182 198 molestyrene/mole LiH* 447.0 109.3 300.8 294.5 276.7 mole sty/hr/mole LiH*163.7 163.7 120.9 120.9 101.5 mole styrene/mole of EB Charged 7.58 1.856.91 6.76 7.57 mole styrene/hr/mole of EB Charged 2.78 2.78 2.78 2.782.78 M_(ncalc) 46486 11372 31290 30634 28781 % Efficiency(M_(ncalc)/M_(n)) • 100% 9980% 2790% 6950% 6840% 6180% Solvent strippedpolymer yield (g) 1168 1729 966 yield % on monomer 90.0% 92.0%  92.8%M_(n) 466 408 450 448 466 M_(w) 675 598 688 702 675 M_(z) 951 932 10501137 951 PD_(n) 1.409 1.559 1.526 1.620 1.409 σ_(n) 312 278 327 337 312_(n)α₃ 2.033 2.993 2.550 2.989 2.033 Dimer strip, polymer yield (g) 9461439 828.4 yield % on monomer 72.9% 76.5%  79.6% M_(n) 536 594 575 M_(w)722 792 753 M_(z) 1049 1091 993 PD_(n) 1.347 1.333 1.310 σ_(n) 316 343320 _(n)α₃ 2.912 2.333 1.933

TABLE VII LOXLSH bimetallic catalyst process: LOXKH and LOXMgH₂. Example25 26 27 28 29 Temp Catalyst Initially Formed 9 9 9 −5 −5 Rxn.Temperature, ° C. 80 80 80 80 80 Hydrogen (psig) 16 13 13 13 47-63Solvent CH CH CH MCH MCH Mass, g 272.7 272.7 272.7 288.8 288.8 vol, ml350 350 350 375.00 375.00 DMEAH (g) 2.45 2.46 2.46 3.32 5.00 moles0.0275 0.0276 0.0276 0.0372 0.0561 Ethlbenzene (g) 91.23 91.23 91.23140.00 140.00 moles 0.86 0.86 0.65 0.86 0.86 vol, ml 105 105 79 105 105TMEDA (g) 3.26 3.26 3.26 6.51 8.61 moles 0.0280 0.0280 0.0281 0.0560.074 vol, ml 4.20 4.20 4.21 8.40 11.11 Dibutylmagnesium, M na na na 1.01.0 vol, ml 0.00 0.00 0.00 7.00 14.02 moles 0.00 0.00 0.00 0.007000.01402 PotassiumHydride (g) 0.55 0.28 0.14 0.00 0.00 moles 0.01380.0069 0.0034 0.00 0.00 Mass of 30% dispersion in mineral oil 1.84 0.920.46 0.00 0.00 n-Butyllithium, M 2.0 2.0 2.0 2.0 2.0 vol, ml 20.61 24.1025.80 24.50 28.05 moles 0.0412 0.0482 0.0516 0.0490 0.05610 Styrene, g990.0 996.9 990.0 1009.0 509.5 moles 9.51 9.57 9.51 9.69 4.89 vol, ml1089 1097 1089 1110 561 feed rate ml/min 7.00 7.00 7.00 7.00 7.00 timeof feed, min 155.6 156.7 155.6 158.6 80.1 feed rate g/min 6.36 6.36 6.366.36 6.36 feed velocity ft/sec 1.89 1.89 1.89 1.89 1.89 Process Scale-UpParameters 0.0275 0.0275 0.0274 0.0257 0.0280 total moles active metalmole Lithium/mole K (or mole Mg) 2.99 7.00 15.00 7.00 4.00 molelithium/mole DMEAH 1.50 1.75 1.87 1.32 1.00 mole DMEAH/mole K (or moleMg) 2.00 4.01 8.02 5.32 4.00 Equivalents metal/mole DMEAH 2.00 2.00 1.991.69 1.50 Mole TMEDA/mole metal 0.510 0.509 0.510 1.001 1.057 Initialhydride conc. (moles/liter) 0.0573 0.0568 0.0598 0.0502 0.0540 molestyrene/mole hydride equivalents 346 348 346 376 174 mole sty/hr/molehydride equivalents 133 133 134 142 131 mole styrene/mole of EB charged11.0 11.1 14.7 11.3 5.7 mole styrene/hr/mole of EB charged 4.26 4.265.68 4.26 4.26 M_(ncalc) 36000 36000 36000 39100 18100 % Efficiency(M_(ncalc)/M_(n)) • 100% 5740% 5250% 6200% 7760% 3762% Solvent strippedpolymer yield (g) 911 935 934 962 492 yield % on monomer  92.0%  93.8% 94.3%  95.3%  96.5% M_(n) 627 689 580 504 481 M_(w) 1066 1051 915 773713 M_(z) 1559 1461 1306 1180 1008 PD_(n) 1.700 1.527 1.578 1.534 1.482σ_(n) 525 500 441 368 334 _(n)α₃ 1.923 1.725 1.867 2.538 1.969 Dimerstrip, polymer yield (g) 829 845 827 825 427 yield % on monomer  84% 85%  84%  82%  84% M_(n) 780 765 717 622 593 M_(w) 1151 1099 997 853805 M_(z) 1582 1486 1335 1207 1116 PD_(n) 1.476 1.437 1.391 1.371 1.358σ_(n) 538 505 448 379 355 _(n)α₃ 1.725 1.667 1.711 2.417 2.256

TABLE VIII Less Preferred LOXLiH monometallic catalyst processes andliving anionic polystyrene initiated with LOXLiH w/termination byhydrogen. Example 30 31 32 33* 34 35 36 37 Catalyst or Initiator Formed(° C.) 20 15 −5 20 20 20 20 20 Rxn. Temperature (° C.) 80 80 80 82 82 8282 82 Reactor Atmosphere H₂ H₂ H₂ CH CH CH CH CH Reactor pressure (psig)55 60 60 0 0 0 0 0 Solvent CH CH MCH CH CH CH CH CH mass (g) 428.5 389.5231.0 506.4 506.4 428.5 506.4 506.4 vol. (ml) 550 500 300 650 650 550650 650 Polarizing complexing agent 2-Methoxyethanol DMAEOEH DMEAHPolarizing complexing agent (g) 2.10 3.80 4.00 6.98 7.02 5.00 5.00 3.02moles 0.0276 0.0285 0.0300 0.0783 0.0788 0.0561 0.0561 0.0339Ethylbenzene (g) 95.00 95.00 136.00 65.00 65.00 65.00 65.00 65.00 moles0.90 0.90 1.28 0.61 0.61 0.61 0.61 0.61 vol. (ml) 110 110 157 75 75 7575 75 TMEDA (g) 3.35 3.35 0.00 0.00 7.12 0.00 6.80 7.90 moles 0.0290.029 0.000 0.000 0.061 0.000 0.059 0.068 vol. (ml) 4.32 4.32 0.00 0.009.19 0.00 8.77 10.19 n-Butyllithium, 2M vol. (ml) 28.77 28.77 22.5458.96 58.40 58.70 58.15 50.90 moles 0.0575 0.0575 0.0451 0.1179 0.11680.1174 0.1163 0.1018 Styrene, g 160.0 131.5 131.5 131.5 130.0 130.9131.5 131.3 moles 1.54 1.26 1.26 1.26 1.25 1.26 1.26 1.26 vol, ml 176145 145 145 143 144 145 144 feed rate ml/min 5.00 5.00 5.00 4.80 4.804.80 4.80 4.80 time of feed, min 35.2 28.9 28.9 30.1 29.8 30.0 30.1 30.1feed rate g/min 4.55 4.55 4.55 4.36 4.36 4.36 4.36 4.36 feed velocityft/sec 1.35 1.35 1.35 1.29 1.29 1.29 1.29 1.29 Process Scale-UpParameters mole lithium/mole polarizing 2.08 2.02 1.50 1.51 1.48 2.092.07 3.00 complexing agent Mole TMEDA/moleLIH 0.96 0.99 0.00 0.00 1.610.00 0.97 1.00 Initial LiH Molarity 0.0432 0.0451 0.0314 0.0505 0.04800.0897 0.0760 0.0864 Initial LiH conc. (ppm) 432 449 308 505 480 896 762868 Final LiH conc. (ppm) 335 357 230 417 398 722 630 717 molestyrene/mole LiH 51.3 43.5 83.9 31.9 32.8 20.5 21.0 18.6 molesty/hr/mole LiH 87.4 90.3 174.1 63.5 66.1 41.0 41.8 37.0 molestyrene/mole EB 1.71 1.41 0.98 2.06 2.04 2.05 2.06 2.06 molestyrene/hr/mole EB 2.92 2.92 2.04 4.10 4.10 4.10 4.10 4.10 polymeryield, g 150 not isolated not isolated 112 125 118 114 128 yield % onmonomer**  94% na. na.  86%  96%  90%  86%  97% M_(n calc) 5338 45288731 3316 3413 2134 2183 1933 % Efficiency (M_(n calc)/M_(n)) · 100% 86%   95% 1172%  49%  67%  35%  26%  11% M_(n) 6179 4755 745 6707 50846148 8447 17972 M_(w) 14,550 183,233 23,605 15,064 15,947 17,445 19,11637,183 M_(z) 22,964 550,722 139,795 21,423 24,967 24,274 26,143 49,015PD_(n) 1.578 3.006 5.922 1.422 1.566 1.391 1.368 1.318 σ_(n) 7192 29,1324127 7487 7432 8334 9493 18581 _(n)α₃ 2.338 18.914 34.431 1.751 2.5591.883 1.560 1.299 *This living anionic polymerization run (Example 33)was terminated transferred to the wash reactor under positive nitrogenpressure applied at the end of the styrene monomer feed. The reactionmass had the characteristic red color of a living anionicpolymerization. The living anionic polymer distributions of Examples(34-37) were terminated with 65PSIG H₂ and then subsequently transferredto the wash reactor after observing a pressure drop of 2-5 PSIG H₂. Thetransferred reaction masses were light pink in color before furtherquenching with water thus indicating termination of most if notessentially all of the living anionic polymer chains by H₂. **Yieldsbelow 100% are the result of sampling as well as hold up of theserelatively high molecular weight polymers in the wash reactor afterstripping ethylbenzene-no evidence of incomplete conversion of styreneor significant formation of ethylbenzene.

TABLE IX Lithium hydride initiated Living APS Distributions Prepared atfrom either: 1) [DMEA⁻]₈Li₁₂H₄ w/ [DMEA⁻]₉Li₁₄H₅ Empirical CatalystComposition; or 2) [DMEA⁻]₁₇Li₂₂H₅ w/ [DMEA⁻]₁₆Li₂₀H₄ Empirical CatalystComposition; Under a Cyclohexane Atmosphere. Example 40 41 Temperature,° C. 77-79 77-79 Atmosphere Cyclohexane Cyclohexane Cyclohexane (psig)−2 to 0 −1 to 0 RPM 1130 1130 Cyclohexane (ml) 500 500 Cyclohexane (g)385 385 Targeted [DMEA⁻]_(x)Li_(y)H_(z) catalyst component ratio[DMEA⁻]₂Li₃H [DMEA⁻]₃Li₄H DMEAH (g) 5.18 5.18 moles 0.0581 0.0581 2Mn-Butyllithium (ml) 44.95 38.64 moles 0.0899 0.0773 Styrene, g 98.0102.0 moles 0.94 0.98 Cyclohexane diluent (g) 90 90 Total Styrene Feedvol. (ml) 200 200 feed rate ml/min 5.00 5.00 time of feed, min 22 22mole Li/mole DMEAH 1.55 1.33 Initial LiH conc. (M) 0.058 0.036 Final LiHconc. (M) 0.050 0.030 Initial LiH conc. (ppm) 594 362 Final LiH conc.(ppm) 483 292 mole styrene/mole LiH 29.6 51.1 M_(ncalc) 3,081 5,318Efficiency (M_(ncalc)/M_(nexp)) 0.22 0.21 Theoretical yield (g) 98 102APS polymer yield (g) 90 90 yield % on Styrene 91.8% 88.2% M_(n) 13,84525,652 M_(w) 38,933 39,057 M_(z) 65,777 61,865 PD_(n) 1.689 1.584 σ_(n)18,637 18,544 _(n)α₃ 2.838 2.923

TABLE X HMAPS Distributions Prepared at 80° C., 1130 RPM Mixing, withFresh Solvents (Cyclohexane and Ethylbenzene); TMEDA with [DMEA⁻]₂Li₃HCatalyst - Demonstrating the Effect of H₂ pressure and Styrene Feed Rateon the HMAPS MWD Formed. Example 42 43 44 45 46 47 H₂ Pressure (psig) 1312 11 10 10 to 9 10 Cyclohexane (g) 233.7 233.7 233.7 233.7 233.7 233.7DMEAH (g) 2.52 2.56 2.51 2.50 2.51 2.50 moles 0.0283 0.0287 0.02820.0280 0.0282 0.0280 Ethybenzene(g) 140.00 140.00 140.00 140.00 146.73160.00 moles 1.32 1.32 1.32 1.32 1.38 1.51 TMEDA (g) 3.40 3.88 3.31 3.333.31 3.30 moles 0.0293 0.0334 0.0285 0.0287 0.0285 0.0284 2M-Butyllithium ml 21.89 21.89 21.26 21.39 21.62 21.13 moles 0.0438 0.04380.0425 0.0428 0.0432 0.0423 Styrene, g 1042.0 1042.0 1064.0 1065.01063.6 1066.4 moles 10.00 10.00 10.22 10.203 10.21 10.24 vol, ml 11461146 1171 1172 1170 1173 feed rate ml/min 7.00 8.00 8.36 8.80 8.80 8.80time of feed, min 164 143 140.01 133 133 133 feed rate g/min 6.36 7.277.60 8.00 8.00 8.00 mole Li/mole DMEAH 1.55 1.52 1.51 1.53 1.54 1.51Mole TMEDA/mole LiH 1.89 2.22 1.98 1.94 1.89 2.00 Initial LiH conc. (M)0.032 0.031 0.030 0.030 0.030 0.028 Final LiH conc. (M) 0.010 0.0100.009 0.010 0.010 0.009 Initial LiH conc. (ppm) 311 302 288 296 298 272Final LiH conc. (ppm) 86 83 78 80 82 76 mole styrene/mole LiH 644.8664.0 711.1 693.9 676.8 720.0 mole sty/hr/mole LiH 236.2 278.0 304.7312.7 305.4 324.0 mole styrene/mole of EB 7.58 7.58 7.73 7.74 7.38 6.78mole styrene/hr/mole of EB 2.78 3.17 3.31 3.49 3.33 3.05 M_(n calc)67,058 69,055 73,954 72,166 70,393 74,878 Efficiency 155.59 163.25160.77 140.13 147.88 150.66 M_(n) 431 423 460 515 476 497 M_(w) 623 611679 781 710 742 M_(z) 899 894 970 1116 1018 1055 PD_(n) 1.443 1.4631.429 1.429 1.434 1.422 σ_(n) 288 282 317 370 334 349 _(n)α₃ 2.282 2.4282.083 1.985 2.075 1.994 M_(w) 10% High 1554 1529 1672 1905 1754 1806Theoretical yield 2084 2129 2130 Solvent stripped 1914 2009 1999 polymeryield, (g) yield % on styrene 91.8% 94.4% 93.9% Dimer stripped 1531 17551743 polymer yield, g yield % on monomer 73.5% 82.4% 81.8% M_(n) 548 593585 M_(w) 705 804 793 M_(z) 930 1085 1072 PD_(n) 1.286 1.356 1.356 σ_(n)293 354 349 _(n)α₃ 2.112 1.947 1.969 M_(w) 10% High 1596 1861 1831Example 48 49 50 51 H₂ Pressure (psig) 9 11 11 10 Cyclohexane (g) 233.7233.7 233.7 233.7 DMEAH (g) 2.52 2.54 2.53 2.53 moles 0.0283 0.02850.0284 0.0284 Ethybenzene(g) 170.00 170.00 170.00 160.00 moles 1.60 1.601.60 1.51 TMEDA (g) 3.37 3.54 3.40 3.67 moles 0.0290 0.0305 0.02930.0316 2M -Butyllithium ml 21.34 21.30 21.25 21.47 moles 0.0427 0.04260.0425 0.0429 Styrene, g 1157.5* 1058.8 1058.7 1059.3 moles 11.11 10.1710.17 10.17 vol, ml 1273 1165 1165 1165 feed rate ml/min 9.40 9.40 10.0010.00 time of feed, min 135 124 116 117 feed rate g/min 8.54 8.54 9.099.09 mole Li/mole DMEAH 1.51 1.50 1.50 1.51 Mole TMEDA/mole LiH 2.012.16 2.07 2.17 Initial LiH conc. (M) 0.028 0.027 0.027 0.028 Final LiHconc. (M) 0.009 0.009 0.009 0.009 Initial LiH conc. (ppm) 269 263 263278 Final LiH conc. (ppm) 72 76 76 78 mole styrene/mole LiH 771.3 720.6720.1 698.8 mole sty/hr/mole LiH 341.6 348.9 371.0 359.8 molestyrene/mole of EB 6.93 6.34 6.34 6.74 mole styrene/hr/mole of EB 3.073.07 3.27 3.47 M_(n calc) 80,216 74,945 74,889 72,677 Efficiency 175.53138.79 142.65 143.63 M_(n) 457 540 525 506 M_(w) 661 815 804 758 M_(z)941 1152 1165 1080 PD_(n) 1.424 1.413 1.449 1.425 σ_(n) 305 385 383 357_(n)α₃ 2.143 1.904 2.075 2.001 M_(w) 10% High 1626 1963 2048 1844Theoretical yield 2216 2118 Solvent stripped 2057 1998 polymer yield,(g) yield % on styrene 92.8% 94.3% Dimer stripped 1798 1800 polymeryield, g yield % on monomer 81.1% 85.0% M_(n) 591 601 M_(w) 800 836M_(z) 1078 1142 PD_(n) 1.354 1.391 σ_(n) 351 376 _(n)α₃ 1.941 1.923M_(w) 10% High 1855 1955

TABLE XI HMAPS Distributions Prepared at 80° C., 1130 RPM Mixing, withFresh Solvents (Cyclohexane Only); w/wo TMEDA with the [DMEA⁻]₂Li₃HCatalyst-Demonstrating the Offsetting Effects of H₂ pressure, StyreneFeed Rate and TMEDA on the HMAPS MWD Formed. Example 52 53 54 55 56 5758 59 H₂ (psig) 10 13-14 13-15 14 15-17 15-17 15-17 14 Cyclohexane (g)389.5 389.5 389.5 389.5 389.5 389.5 389.5 389.5 DMEAH moles 0.02840.0284 0.0285 0.0284 0.0286 0.0286 0.0285 0.0286 TMEDA (g) 3.67 3.513.67 3.51 1.80 1.80 0.00 0.00 moles 0.0316 0.0302 0.0316 0.0302 0.01550.0155 0.0000 0.0000 2 M n-Butyllithium(ml) 21.25 21.25 21.51 21.5121.38 21.38 21.47 21.64 moles 0.0425 0.0425 0.0430 0.0430 0.0428 0.04280.0429 0.0433 Styrene, g 1058.7 1060.0 1060.0 1060.0 1060.0 1059.01061.0 1063.7 moles 10.17 10.18 10.18 10.18 10.18 10.17 10.19 10.21 vol,ml 1165 1166 1166 1166 1166 1165 1167 1170 feed rate ml/min 9.40 9.4010.00 10.00 9.40 10.00 10.00 10.00 time of feed, min 124 124 117 117 124117 117 117 feed rate g/min 8.54 8.54 9.09 9.09 8.54 9.09 9.09 9.09 moleLi/mole DMEAH 1.50 1.50 1.51 1.52 1.49 1.49 1.51 1.51 Mole TMEDA/moleLiH 2.24 2.14 2.18 2.06 1.09 1.09 0.00 0.00 Initial LiH conc. (M) 0.0270.027 0.028 0.028 0.027 0.027 0.028 0.028 Final LiH conc. (M) 0.0090.009 0.009 0.009 0.009 0.009 0.009 0.009 Initial LiH conc. (ppm) 272272 280 282 274 274 281 285 Final LiH conc. (ppm) 76 76 78 79 77 77 7879 mole styrene/mole LiH 720.1 721.0 700.9 695.6 719.3 718.6 705.4 696.4mole sty/hr/mole LiH 348.7 348.7 360.7 357.9 347.9 370.1 362.6 357.1M_(n calc) 74,889 74,981 72,900 72,341 74,805 74,735 73,359 72,430Efficiency 133.97 134.37 122.73 125.16 136.76 121.32 128.70 124.02 M_(n)559 558 594 578 547 616 570 584 M_(w) 847 863 927 907 849 958 890 909M_(z) 1189 1245 1309 1299 1208 1330 1276 1286 PD_(n) 1.404 1.443 1.4121.432 1.423 1.388 1.434 1.415 σ_(n) 401 413 445 436 406 459 427 436_(n)α₃ 1.831 2.007 1.804 1.907 1.880 1.673 1.928 1.826 M_(w) 10% High2012 2131 2199 2203 2046 2207 2168 2166 Theoretical yield 2119 2120 21192125 Solvent stripped 2027 2033 2029 2054 polymer yield, (g) yield % onstyrene 95.7% 95.9% 95.8% 96.6% Dimer stripped polymer 1824 1846 18251826 yield, g yield % on monomer 86.1% 87.1% 86.1% 85.9% M_(n) 670 699715 704 M_(w) 924 993 990 984 M_(z) 1234 1343 1313 1334 PD_(n) 1.3791.421 1.385 1.398 σ_(n) 413 453 443 444 _(n)α₃ 1.725 1.714 1.630 1.815M_(w) 10% High 2116 2266 2194 2268

TABLE XII HMAPS Distributions Prepared at 80°-90° C., 1130 or 1000 RPMMixing, with Partial Recycle Solvents (Cyclohexane and Ethylbenzene)with the [DMEA⁻]₂Li₃H Catalyst Example 60 61 62 63 64 65 66 67 CatalystAging Time (min) 60 90 45 120 135 95 15 170 H₂ (psig) 11-12 16-13 14 1613-15 13-15 18 17-19 Temperature, ° C. 80 80 80 86*  90 90 90 90Agitator RPM 1130 1130 1000 1000 1000 1000 1000 1000 Recycle Solvent(ml) 320 320 340 320 320 320 320 320 Cyclohexane (g) 200.6 200.6 213. 2200.6 200.6 200.6 200.6 233.8 Ethylbenzene (g) 52.05 52.05 55.30 52.0552.05 52.05 52.05 17.17 DMEAH moles 0.0285 0.0230* 0.0286 0.0286 0.02850.0284 0.0285 0.0285 Fresh Cyclohexane to form 140 140 140 140 140 140140 140 catalyst (g) 2 M n-Butyllithium (ml) 21.67 17.60 21.67 21.6421.42 21.52 21.48 21.42 moles 0.0433 0.0352 0.0433 0.0433 0.0428 0.04300.0430 0.0428 Styrene, g 1061.0 1061.0 1041.0 1008.0 1015.0 1035.81040.1 1045.8 moles 10.19 10.19 10.00 968 9.75 9.95 9.99 10.04 vol, ml1167 1167 1145 1109 1117 1139 1144 1150 feed rate ml/min 10.00 10.0010.0 10.00 9.40 9.40 9.40 9.40 time of feed, min 117 117 115 111 119 121122 122 feed rate g/min 9.09 9.09 9.09 9.09 8.54 8.54 8.54 8.54 moleLi/mole DMEAH 1.52 1.53 1.52 1.51 1.50 1.52 1.51 1.50 Initial LiH conc.(M) 0.0285 0.0236 0.0272 0.0281 0.0275 0.0281 0.0278 0.0276 Final LiHconc. (M) 0.009 0.008 0.009 0.010 0.009 0.009 0.009 0.009 Initial LiHconc. (ppm) 287 238 274 283 277 283 279 278 Final LiH conc. (ppm) 80 6680 82 80 80 79 78 mole styrene/mole LiH 685.8 834.2 678.0 660.0 679.6678.5 690.2 700.3 mole sty/hr/mole LiH 352.5 428.8 355.2 357.1 343.3335.8 340.2 343.3 mole styrene/mole of EB 20.75 20.75 19.16 19.71 19.8520.25 20.34 61.99 mole styrene/hr/mole of EB 10.66 10.66 10.04 10.6610.02 10.02 10.02 30.39 M_(n calc) 71,324 86,756 70,512 68,637 70,68370,566 71,786 72,828 Efficiency 121.09 140.84 107.49 116.93 128.52126.46 115.60 126.00 M_(n) 589 616 656 587 550 558 621 578 M_(w) 9271012 1026 900 835 848 974 911 M_(z) 1328 1517 1424 1254 1173 1188 13731325 PD_(n) 1.433 1.499 1.388 1.393 1.405 1.401 1.410 1.454 σ_(n) 446494 493 429 396 402 468 439 _(n)α₃ 1.902 2.168 1.660 1.735 1.832 1.8051.779 2.023 M_(w) 10% High 2253 2629 2360 2100 1982 2003 2304 2267Theoretical yield 2122 2049 2051 2086 Solvent stripped polymer yield,(g) 2040 1960 1947 1989 yield % on styrene 96.1% 95.6% 94.9% 95.4% Dimerstripped polymer yield, g 1856 1776 1716 1819 yield % on styrene 87.5%86.7% 83.7% 87.2% M_(n) 725 764 695 701 M_(w) 1053 1052 935 1007 M_(z)1494 1386 1228 1385 PD_(n) 1.452 1.377 1.345 1.437 σ_(n) 488 469 408 463_(n)α₃ 2.089 1.586 1.681 1.833 M_(w) 10% High 2602 2307 2064 2355

TABLE XIII HMAPS Distributions Prepared at 90° C., 1065 to 950 RPMMixing, with 100% Recycle Solvents (Cyclohexane and Ethylbenzene) withthe [DMEA⁻]₂Li₃H Catalyst. Example 68 69 70 71 72 73 74 Catalyst AgingTime (min) 338 120 180 120 150 150 120 Catalyst Combined intial 800,16-20 800, 16-20 800, 16-20 800, 16-20 800, 16-20 500, 16-20 200, 2 RPMand psig H₂ (psig) 13 14 16-17 (25) 17 15-17 (18) 14 9-11 RPM (HMAPSProcess) 1000 1000 950 (1000) 950 950 (975) 950 1065 Total RecycleSolvent (ml) 498 498 498 498 500 500 500 Cyclohexane (g) 364.3 364.3364.3 364.3 333.2 333.2 333.2 Ethylbenzene g 26.74 26.74 26.74 26.7458.80 58.80 58.80 DMEAH moles 0.0282 0.0283 0.0285 0.0284 0.0285 0.02850.0285 2 M n-Butyllithium (ml) 21.40 21.42 21.42 21.47 21.42 21.47 21.47moles 0.0428 0.0428 0.0428 0.0429 0.0428 0.0429 0.0429 Styrene, g 1040.11060.1 1045.0 890.0 1000.0 911.3 1041.8 moles 9.99 10.18 10.03 8.55 9.608.75 10.00 vol, ml 1144 1166 1150 979 1100 1003 1146 feed rate ml/min9.40 9.40 9.00 9.00 9.00 9.00 9.70 time of feed, min 122 124 128 109 122111 118 feed rate g/min 8.54 8.54 8.18 8.18 8.18 8.18 8.82 mole Li/moleDMEAH 1.52 1.52 1.50 1.51 1.50 1.51 1.51 Initial LiH conc. (M) 0.02820.0280 0.0276 0.0280 0.0275 0.0277 0.0277 Final LiH conc. (M) 0.0090.009 0.009 0.010 0.009 0.010 0.009 Initial LiH conc. (ppm) 284 282 278282 277 279 279 Final LiH conc. (ppm) 80 79 78 89 81 87 79 molestyrene/mole LiH 681.7 698.9 699.7 587.1 669.6 605.8 692.6 molesty/hr/mole LiH 336.0 338.0 328.7 323.8 328.7 326.3 351.7 molestyrene/mole of EB 39.58 40.34 39.77 33.87 17.31 15.77 18.03 molestyrene/hr/mole of EB 19.51 19.51 18.68 18.68 8.50 8.50 9.16 M_(n calc)70,895 72,687 72,772 61,062 69,639 63,009 72,032 Efficiency 133.26136.37 135.52 119.97 143.58 131.27 136.68 M_(n) 532 533 537 509 485 480527 M_(w) 813 826 925 773 747 710 1021 M_(z) 1167 1211 1559 1108 11331009 1878 PD_(n) 1.435 1.466 1.685 1.433 1.517 1.421 1.839 σ_(n) 387 395456 367 356 332 510 _(n)α₃ 2.000 2.139 2.985 2.007 2.462 2.025 3.407M_(w) 10% High 1992 2083 2802 1897 1965 1732 3323 Theoretical yield 21001935 1911 1042 Solvent stripped 1993 1816 1787 959 polymer yield, (g)yield % on styrene 94.9% 93.9% 93.5% 92.0 Dimer stripped polymer 17871623 1574 852 yield, g yield % on styrene 85.1% 83.9% 82.4% 81.8 M_(n)648 646 591 675 M_(w) 899 939 817 1145 M_(z) 1230 1404 1149 1946 PD _(n)1.387 1.454 1.382 1.696 σ_(n) 403 435 365 563 _(n)α₃ 1.955 2.614 2.2853.101 M_(w) 10% High 2111 2498 1998 3484

TABLE XIII HMAPS Distributions Prepared at 80° C., 1130 RPM Mixing, with100% Recycle Solvents (Cyclohexane and Ethylbenzene) or with FreshMethylcyclohexane (w/wo Ethylbenzene) with the [DMEA⁻]₂Li₃HCatalyst—Demonstrating the Offsetting Effects of Catalyst Concentration,Solvent, H₂ pressure, Styrene Feed Rate and Mixing on the HMAPS MWDformed. Example 75 76 77 78 79 Feed tip Diameter (cm) 0.12 0.12 0.120.12 0.051 Feed tip Diameter (inches) 0.045 0.045 0.045 0.045 0.020 H₂,(psig) 19 19-21 19-21 15 15-11 Solvent Recycle CH Recycle CH Recycle CHMCH MCH & EB Cycloaliphatic hydrocarbon (g) 399.9 227.1 320.2 396.4246.4 Ethylbenzene (g) 70.56 39.40 71.73 0.00 156.00 Total Solvent vol.(ml) 600* 500 500 515 500 DMEAH, moles 0.0286 0.0285 0.0285 0.02860.0286 2M n-Butylllithium vol (ml) 21.52 21.48 21.48 21.52 21.52 moles0.0430 0.0430 0.0430 0.0430 0.0430 Styrene, g 940.0 1041.8 941.8 941.81023.9 moles 9.03 10.00 9.04 9.04 9.83 vol, ml 1034 1146 1036 1036 1126feed rate ml/min 10.00 10.00 9.40 9.40 10.00 time of feed, min 103 115110 110 113 feed rate g/min 9.09 9.09 8.54 8.54 9.09 mole Li/mole DMEAH1.50 1.51 1.51 1.50 1.50 Initial LiH conc. (M) 0.0232 0.0278 0.02780.0269 0.0277 Final LiH conc. (M) 0.009 0.009 0.010 0.010 0.009 InitialLiH conc. (ppm) 234 278 280 276 272 Final LiH conc. (ppm) 80 79 85 85 79mole styrene/mole LiH 625.3 691.4 625.0 626.5 681.1 mole sty/hr/mole LiH362.8 361.9 340.2 341.0 362.8 mole styrene/mole of EB 13.56 26.91 13.36n.a. 6.68 mole styrene/hr/mole of EB 7.87 14.09 7.27 n.a. 3.56 Example(continued) 75 76 77 78 79 M_(ncalc) 65,035 71,904 65,002 65,159 70,839Efficiency 115.31 120.24 109.99 123.88 138.63 M_(n) 564 598 591 526 511M_(w) 889 941 907 831 767 M_(z) 1313 1359 1268 1255 1096 PD_(n) 1.4771.444 1.398 1.510 1.429 σ_(n) 428 453 432 401 362 _(n)α₃ 2.151 1.9691.761 2.332 2.020 M_(w), 10% High 2260 2307 2125 2186 1871 Theoreticalyield 940 1042 942 942 1024 Solvent stripped 896 994 899 884 961 polymeryield, (g) yield % on styrene 95.3% 95.4% 95.5% 93.9% 93.9% Dimerstripped polymer yield, g 810 918 837 793 871 yield % on styrene 86.2%88.1% 88.9% 84.2% 85.1% M_(n) 676 708 682 665 627 M_(w) 964 1004 946 940855 M_(z) 1354 1380 1242 1347 1163 PD_(n) 1.426 1.418 1.387 1.414 1.364σ_(n) 441 458 424 428 378 _(n)α₃ 2.079 1.886 1.515 2.341 1.999 M_(w) 10%High 2346 2354 2056 2364 1995

TABLE IV LOXLiH catalyst process Examples with ca. 1/2 styrene monomerfeed without use of a promotor (i.e. TMEDA free). Example 6 7 8 9 10 1112 13 Temp Catalyst Initially 20 34 40 40 55 40 40 35 Formed (° C.) Rxn.Temperature (° C.) 80 80 80 80 80 80 80 80 Hydrogen (PSIG) 59-31 59-3165-31 17-36 15-17 15 15 15 Cyclohexane (g) 311.6 311.6 311.6 311.6 311.6311.6 311.6 311.6 vol. (ml) 400 400 400 400 400 400 400 400 DMEAH (g)2.34 2.38 3.40 3.42 2.37 4.60 4.60 4.60 moles 0.0263 0.0267 0.03810.0384 0.0266 0.0516 0.0516 0.0516 Ethylbenzene (g) 106.00 106.00 106.00110.00 120.00 100.00 100.00 100.00 moles 1.00 1.00 1.00 1.04 1.13 0.940.94 0.94 vol. (ml) 122 122 122 127 138 115 115 115 n-Butyllithium, M2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 vol. (ml) 28.59 29.25 28.59 29.23 20.2839.28 39.02 38.87 moles 0.0572 0.0585 0.0572 0.0585 0.0406 0.0786 0.07800.0777 Styrene, g 447.0 452.6 471.0 519.5 546.5 512.8 406.2 219.5 moles4.29 4.35 4.52 4.99 5.25 4.92 3.90 2.11 vol. (ml) 492 498 518 572 601564 447 241 feed rate (ml/min.) 7.00 5.00 5.00 5.00 5.00 7.00 5.57 4.00time of feed (min.) 70.2 99.6 103.6 114.3 120.2 80.6 80.2 60.4 feed rate(g/min.) 6.36 4.55 4.55 4.55 4.55 6.36 5.06 3.64 feed velocity (ft/sec.)1.89 1.35 1.35 1.35 1.35 1.89 1.50 1.08 Process Scale-Up Parameters moleorganolithium/mole 2.18 2.19 1.50 1.52 1.53 1.52 1.51 1.51 DMEAH InitialLiH* conc. ppm 0.056 0.058 0.035 0.036 0.025 0.049 0.048 0.047 InitialLiH* conc. M 556 571 342 357 247 480 471 465 Final LiH* conc. ppm 277282 166 165 112*   223 247 312 Final LiH* conc., M 0.028 0.029 0.0170.017 0.011* 0.023 0.025 0.032 mole styrene/mole LiH* 138.8 136.7 237.5248.1 375.3 182.7 147.5 80.7 mole sty/hr/mole LiH* 118.5 82.4 137.5130.3 187.3 136.0 110.3 80.2 mole styrene/mole of EB 4.29 4.35 4.52 4.814.64 5.22 4.13 2.23 mole styrene/hr /mole of EB 3.67 2.62 2.62 2.52 2.313.89 3.09 2.22 M_(n calc) 14,433 14,217 24,706 25,808 39,037 18,99915,343 8390 % Efficiency (M_(n calc)/ 3600%  4000%  6640%  6520%  8070% 5280%  4420%  2640%  M_(n)) · 100% Solvent stripped polymer 777 1306 910yield (g) yield % on monomer 86.4% 85.0% 79.9% M_(n) 402 356 372 396 484360 347 318 M_(w) 564 476 513 601 4722 506 462 408 M_(z) 809 663 7281002 38108* 746 641 545 PD_(n) 1.434 1.393 1.419 1.667 8.070 1.474 1.3871.336 σ_(n) 255 207 229 285 1432 229 200 169 _(n)α₃ 2.402 2.447 2.4073.456 28.594* 2.695 2.438 2.323 Dimer strip, polymer yield (g) 575.341015.71 606.32 yield % on monomer 64% 66% 53% M_(n) 519 578 494 M_(w)639 2556 602 M_(z) 826 31565 761 PD_(n) 1.231 4.422 1.219 σ_(n) 250 1069231 _(n)α₃ 2.391 36.368* 2.166 *Hydrogen uptake became exceedingly slowduring the last 25 minutes of monomer feed consequently a high molecularweight tail formed as part of the MWD.

1. A process of conducting hydrogen mediated saline hydride initiatedpolymerizations which features feeding one or more anionicallypolymerizable hydrocarbon monomers to a reaction medium containing asolvent, a soluble saline hydride catalyst, and optionally apolytertiaryamine compound under an atmosphere comprising molecularhydrogen.
 2. The process of claim 1, wherein the soluble saline hydridecatalyst comprises a soluble saline hydride LOXSH catalyst formed fromreagents comprising (i) molecular hydrogen; (ii) an organolithiumcompound and/or an organomagnesium compound; (iii) optionally apolytertiaryamine compound; (iv) a polarizing complexing agent selectedfrom a tertiary aminoalcohol compound; a tertiary amino ether-alcohol,an ether-alcohol or combinations thereof; (v) optionally an alkali metalor metal alloy and/or a solid saline hydride and/or a saline metalamide; (vi) optionally an aromatic hydrocarbon having at least one C—Hcovalent bond pK_(a) within the range of 2.75 pK_(a) units above that ofthe pK_(a) of toluene to −4.30 pK_(a) units below the pK_(a) of toluene;and (vii) a hydrocarbon solvent with a pK_(a) greater than H₂; whereinthe aromatic hydrocarbon and hydrocarbon solvent may be the same ordifferent.
 3. The process of claim 1, wherein the anionicallypolymerizable hydrocarbon monomers comprises a vinyl aromatic monomer.4. The process of claim 1, wherein the anionically polymerizablehydrocarbon monomers comprises styrene; o-, m-, and/or p-isomers ofmethyl styrene; p-isopropylstyrene; 2,4-di ethyl styrene; o-ethylstyrene; 3,5-di-isobutylstyrene; 2,6-dimethylstyrene; and/or2-ethyl-4-methyl styrene.
 5. The process of claim 1, wherein theanionically polymerizable hydrocarbon mononers comprises one or moreof 1) a vinyl aromatic monomer and a styrenic monomer; and/or 2) astyrenic monomer and styrene; and/or 3) styrene.
 6. The process of claim2, wherein the anionically polymerizable hydrocarbon monomers comprisesstyrene.
 7. The process of claim 1, wherein the reaction mediumcomprises a hydrocarbon solvent with a pK_(a) greater than that of H₂.8. The process of claim 1, wherein the partial pressure of molecularhydrogen is maintained at pressures between about 0.5 Bar to about 19.0Bar.
 9. The process of claim 1, wherein the temperature of the processis maintained in the range of about 20° C. to about 130° C.
 10. Theprocess of claim 1, wherein the molar ratio of the total charge ofmonomer to soluble saline hydride catalyst initially formed is about10:1 to about 1000:1.
 11. The process of claim 2, wherein the monomercomprises styrene; the soluble saline hydride comprises a LOXLiHcatalyst formed from the reagents comprising molecular hydrogen, anorganolithium compound, optionally TMEDA, N,N-dimethylethanolamine in ahydrocarbon solvent reaction medium comprising one or more ofethylbenzene, cyclohexane and methylcyclohexane; the polymerizationtemperature is maintained between about 20° C. and less than about 100°C.; the partial pressure of molecular hydrogen is maintained betweenabout 0.5 Bar to about 6.0 Bar; and the molar ratio of the total chargeof monomer to soluble saline hydride catalyst initially formed is about10:1 to about 600:1.
 12. The process of claim 11, wherein the solublesaline hydride catalyst comprises a LOXLiH catalyst and has the chemicalformula [DMEA⁻]_(x)Li_(y)H_(z), wherein the LOXLiH catalyst is formedfrom the process of contacting: (i) about y equivalents of anorganolithium compound; (ii) optionally TMEDA compound; (iii) about xequivalents of N,N-dimethylaminoethanol; (iv) optionally ethylbenzene;(v) a hydrocarbon solvent with a pK_(a) greater than H₂; and (vi)molecular hydrogen, wherein the amount of hydride formed z is given bythe equation z=y−x and x, y and z are positive real numbers whole orfractional greater than zero; wherein the formula can further compriseN,N,N′,N′-tetramethylethylenediamine (TMEDA) ligand complex i.e.[DMEA⁻]_(x)Li_(y)H_(z) XTMEDA in a molar ratio of X moles TMEDA per moleof catalyst [DMEA⁻]_(x)Li_(y)H_(z) wherein X=0.0001 to about 8.0. 13.The process of claim 2 wherein the monomer comprises styrene; the salinehydride LOXSH catalyst comprises a bimetallic LOXMgH₂ catalyst formedfrom the reagents comprising molecular hydrogen, an organolithiumcompound and an organomagnesium compound, optionally TMEDA,N,N-dimethylethanolamine in a hydrocarbon solvent reaction mediumcomprising one or more of ethylbenzene, cyclohexane andmethylcyclohexane; the polymerization temperature is maintained between20° C. and 90° C.; the partial pressure of molecular hydrogen ismaintained between about 0.5 Bar to about 6.0 Bar; and the molar ratioof the total charge of monomer to soluble saline hydride catalystinitially formed is about 10:1 to about 600:1.
 14. The process of claim2, wherein the soluble saline hydride LOXSH catalyst comprises ahydrocarbon soluble LOXLiH catalyst, and the organolithium compoundcomprises one or more of n-butyllithium, sec-butyllithium,t-butyllithium, allyllithium, vinyllithium, phenyllithium,1-hexyl-1-phenyllithium, 1-hexyl-1,1-diphenyllithium, cyclohexyllithium,and/or poly(styryl)lithium compounds which can be added or generated insitu.
 15. The process of claim 2, wherein the soluble saline hydrideLOXSH catalyst comprises a hydrocarbon soluble LOXMgH₂ catalyst, and theorganomagnesium compound comprises one or more butylethylmagnesium(BEM), di-n-butylmagnesium (DBM), n-butyl-n-octylmagnesium,di-n-octylmagnesium, di-cyclohexylmagnesium, and/orpoly(styryl)magnesium compounds which can be added or generated in situ.16. The process of claim 2, wherein the soluble saline hydride catalystcomprises a soluble saline hydride LOXSH catalyst formed from thereagents comprising (i) molecular hydrogen; (ii) an organolithiumcompound with or without an organomagnesium compound; (iii) optionally apolytertiaryamine compound PTA promoter wherein the promoter is one ormore of N,N,N′,N′-tetramethylethylenediamine (TMEDA),N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA), sparteine,isosparteine, and/or 1,4-methylpiperazine; (iv) a polarizing complexingagent selected from: N,N-dimethylaminoethanol, N,N-diethylaminoethanol,N-methyl-di ethanolamine, 3-dimethylamino-1-propanol,2-[2-(dimethylamino)ethoxy] ethanol, 1-(2-hydroxyethyl)piperidine,1-(2-hydroxyethyl)morpholine, 1-(2-hydroxyethyl)pyrolidine, or1-methyl-2-pyrrolidinemethanol or combinations thereof; (v) optionallyan alkali metal or metal alloy and/or a solid saline hydride and/or asaline metal amide; (vi) optionally an aromatic hydrocarbon having atleast one C—H covalent bond pK_(a) within the range of 2.75 pK_(a) unitsabove that of the pK_(a) of toluene to −4.30 pK_(a) units below thepK_(a) of toluene wherein the aromatic hydrocarbon is at least one ofbenzene, toluene, mesitylene, ethylbenzene, n-propylbenzene,n-butylbenzene, iso-butylbenzene, amylbenzene, 1.2-darylethanes,1,3-diarylpropanes, cumene, t-butylbenzene, 1-alkyl naphthalene,2-alkylnaphthalene, a styrene dimer or low molecular weight styreneoligomer distribution; and (vii) a hydrocarbon solvent with a pK_(a)greater than H₂; wherein the aromatic hydrocarbon and hydrocarbonsolvent may be the same or different.
 17. The process of claim 2,wherein the soluble LOXSH catalyst comprises the polytertiaryamine (PTA)promotor and is formed using an alkali metal or metal alloy and/or asolid saline hydride and/or a saline metal amide wherein the molar ratioof the PTA to the total alkali metal and alkali earth metal charged informing LOXSH catalyst is 1:10,000 to about 8:1.
 18. The process ofclaim 2 wherein the polarizing complexing agent comprises at least oneof the structures:

wherein R is independently an organic group forming bonds with one ormore tertiary amines and one hydroxyl, R¹ is independently an organicgroup which may also be further substituted by other tertiary amines, Σis: i) O or NR¹ for I, II, III, IV, V and VI; and ii) O or NR¹ or CH₂for VII; and the index value n is independently a whole number equal toor greater than
 0. 19. The process of claim 2 wherein the polarizingcomplexing agent comprises at least one aminoalcohol selected from:dimethylaminoethanol, diethylaminoethanol, N-methyl-diethanolamine,3-dimethylamino-1-propanol, 2-[2-(dimethylamino)ethoxy]ethanol,1-(2-hydroxyethyl)piperidine, 1-(2-hydroxyethyl)morpholine,1-(2-hydroxyethyl)pyrolidine, or 1-methyl-2-pyrolidinemethanol.
 20. Theprocess of claim 2 wherein the PTA promotors comprises at least one ofN,N,N′,N′-tetramethylethylenediamine (TMEDA),N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA), sparteine,isosparteine, and 1,4-methylpiperazine.
 21. The process of claim 2,wherein the catalyst has the empirical chemical formula: a)[PCA⁻]₄Li₆H₂; b) [PCA⁻]₄Li₈H₄; c) [PCA⁻]₂Li₆H₄; d) [PCA⁻]₄Li₁₂H₈; e)[PCA⁻]₅Li₁₅H₁₀; f) [PCA⁻]₅Li₁₂H₇; g) [PCA⁻]₂Li₅H₃; h) [PCA⁻]₄Li₄MgH₂; i)[PCA⁻]₄Li₄Mg₂H₄; j) [PCA⁻]₂Li₄MgH₄; k) [PCA⁻]₄Li₆Mg₃H₈; l)[PCA⁻]₅Li₉Mg₃H₁₀; m) [PCA⁻]₅Li₆Mg₃H₇; n) [PCA⁻]₂Li₃MgH₃; o)[PCA⁻]₄Li₅KH₂; p) [PCA⁻]₄Li₇KH₄; and q) [PCA⁻]₂Li₅KH₄, wherein [PCA⁻]independently denotes the alkoxide of the corresponding polarizingcomplexing agent reagent alcohol having given up one proton to a morebasic species and wherein said empirical chemical formula can optionallyfurther comprise a PTA ligand complex in a molar ratio of total alkaliand alkali earth metal to PTA from about 10,000 to 1.0 to about 1.0 toabout 8.0.
 22. The process of claim 21, wherein [PCA⁻] comprisesindependently [DMEA⁻], [DMAEOE⁻] or [MEOE⁻].